EP4688695A1 - Mousse inorganique à base de ciment portland ordinaire - Google Patents

Mousse inorganique à base de ciment portland ordinaire

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Publication number
EP4688695A1
EP4688695A1 EP24718060.7A EP24718060A EP4688695A1 EP 4688695 A1 EP4688695 A1 EP 4688695A1 EP 24718060 A EP24718060 A EP 24718060A EP 4688695 A1 EP4688695 A1 EP 4688695A1
Authority
EP
European Patent Office
Prior art keywords
group
source
foam
acid
cementitious slurry
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
EP24718060.7A
Other languages
German (de)
English (en)
Inventor
Ramzi FARRA
Nils Erich Karl MOHRI
Kai Steffen WELDERT
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sika Technology AG
Original Assignee
Sika Technology 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 Sika Technology AG filed Critical Sika Technology AG
Publication of EP4688695A1 publication Critical patent/EP4688695A1/fr
Pending legal-status Critical Current

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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
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/10—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by using foaming agents or by using mechanical means, e.g. adding preformed foam
    • 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
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/10—Coating or impregnating
    • C04B20/1018—Coating or impregnating with organic materials
    • C04B20/1022—Non-macromolecular compounds
    • 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
    • C04B28/04—Portland 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
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/02—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by adding chemical blowing agents
    • 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
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/20—Retarders
    • C04B2103/22—Set retarders
    • 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
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/28—Fire resistance, i.e. materials resistant to accidental fires or high temperatures
    • 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
    • C04B2111/52—Sound-insulating materials

Definitions

  • the present invention relates to a process for preparing an inorganic foam based on a Portland cement clinker-based cementitious binder, to the inorganic foams thus obtained and to elements of construction comprising these inorganic foams.
  • Inorganic foams also named mineral foams or cement foams, combine advantageous properties such as very low specific weight compared to traditional concrete or other building materials.
  • the foam comprises bubbles more or less distant from each other that are gas pockets contained in a solid envelope of mineral binder. Due to the cells or empty spaces that it comprises, it is a material that is significantly lighter than traditional concrete.
  • Inorganic foams can be used as insulation material, e.g., as a thermal insulator, acoustic insulator or acoustic absorber as well as construction material with a low density.
  • Advantages of using inorganic foams lie in the reduced CO2 footprint compared to organic (PU, EPS) and other inorganic (AAC, mineral wool) materials, better health and safety properties, no limitation of application due to possible fire classes, recyclability to 100% in the mineral material circle and higher flexibility by a flexible variation of density depending on application. Additionally, lower energy requirements for raw materials and production reduces impact of product cost in face of rising energy prices of limited resources.
  • inorganic foams are mainly produced using surfactants or proteins as air stabilizer.
  • WO 2018/162381 relates to a process for preparing a particle-stabilized inorganic foam based on calcium sulfoaluminate, to a particle-stabilized inorganic foam based on calcium sulfoaluminate, to a cellular material obtainable by hardening and optionally drying the particle-stabilized inorganic foam based on calcium sulfoaluminate, and to a composition for preparing an inorganic foam formulation for providing a particle- stabilized inorganic foam based on calcium sulfoaluminate.
  • the invention also addresses the issue of long open times to allow reduced turnover times.
  • the objective of the present invention is solved by a method as claimed in claim 1. Further aspects of the invention are the subject of independent claims. Preferred embodiments are the subject of dependent claims. Detailed Ways
  • the invention relates to a method for preparing a mineral foam comprising: a. providing an aqueous cementitious slurry comprising a cementitious binder, a foam-stabilizing agent, and a set control agent; b. foaming the cementitious slurry; wherein the set control agent comprises (i) an ⁇ -hydroxy monocarboxylic acid or a salt thereof and (ii) an oxyanion source selected from the group consisting of a borate source and a carbonate source.
  • the set control/ accelerator combination allows for fast demolding and reduced turnover times. By splitting the process in two stages, the cementitious slurry typically has a long open time, but sets rapidly when the accelerator agent solution is added. This reduces cycle times and maximizes mold usage. Addition of the accelerator agent solution ensures fast strength increase and allows for faster demolding shortly after filling in the mold.
  • Set control agent comprises (i) an ⁇ -hydroxy monocarboxylic acid or a salt thereof and (ii) an oxyanion source selected from the group consisting of a borate source and a carbonate source.
  • the carbonate source is selected from the group consisting of inorganic carbonates having an aqueous solubility of 0.1 g ⁇ L -1 or more, organic carbonates, and mixtures thereof. It is believed that the component (i) an ⁇ -hydroxy monocarboxylic acid or a salt thereof in combination with (ii) an oxyanion source selected from the group consisting of a borate source and a carbonate source retard the formation of ettringite from the aluminate phases originating from the cementitious binder. Suitable ⁇ -hydroxy monocarboxylic acids and salts thereof and include glycolic acid, gluconic acid, lactic acid, 2,3-dihydroxypropanoic acid, and their salts and mixtures thereof.
  • borate or carbonate source ensures that the mixing water is initially highly concentrated in borate or carbonate ions. Borate or carbonate ions are believed to adsorb onto mineral phase surfaces along with the ⁇ -hydroxy monocarboxylic acid or salt thereof. The latter will also partly remain in the pore solution and initially prevent ettringite to be formed.
  • the amount of the oxyanion source may be in the range of from 0.1 to 3 wt.-%, preferably 0.5 to 2.0 wt.-%, more preferably 0.5 to 1 wt.-%, relative to the amount of cementitious binder.
  • the borate source usually comprises a rapidly soluble, inexpensive, borate compound.
  • Suitable borate sources include borax, boric acid, colemanite, and hexahydroborate, and mixtures thereof. Only carbonate sources having a sufficient degree of aqueous solubility are suitable for achieving the desired effect.
  • the carbonate source may be an inorganic carbonate having an aqueous solubility of 0.1 g ⁇ L -1 or more at 25°C.
  • the aqueous solubility of the inorganic carbonate is suitably determined in water with a starting pH value of 7. It is understood that the pH value at the solubility limit is higher than the starting pH value.
  • the organic carbonate is selected from the group consisting of ethylene carbonate, propylene carbonate, glycerol carbonate, dimethyl carbonate, di(hydroxyethyl)carbonate, and mixtures thereof. Preference is given to ethylene carbonate, propylene carbonate, glycerol carbonate, and mixtures thereof, in particular ethylene carbonate and/or propylene carbonate. Mixtures of inorganic carbonates and organic carbonates can as well be used.
  • the set control agent additionally comprises a polymeric polycarboxylic acid.
  • polymeric polycarboxylic acid includes polymeric compounds constituted of monomeric units incorporating carboxylic acid functionalities, and, optionally, further monomeric units.
  • the polymeric polycarboxylic acid can be employed as the free acid or in a partially or completely neutralized form, i.e., as a salt.
  • the cation is not particularly limited and may be selected from the group consisting of alkali metals, such as sodium or potassium, and ammonium cations.
  • the polycarboxylic acid has a carboxylic acid equivalent weight of 333 or less. The carboxylic acid equivalent weight can be determined by weighing in a sample of the polymeric polycarboxylic acid and titration of the carboxylic acid groups.
  • the molecular weight of the polymeric polycarboxylic acids is 25,000 g/mol or less, preferably the molecular weight is in the range of 1,000 to 25,000 g/mol, most preferably 1,000 to 5,000 g/mol.
  • Effective polymeric polycarboxylic acids have a carboxylic group density within a certain range.
  • the milliequivalent number is 3.0 meq/g or higher, preferably 3.0 to 17.0 meq/g, more preferably 5.0 to 17.0 meq/g, most preferably 5.0 to 14.0 meq/g.
  • the polymeric polycarboxylic acid can be employed as the free acid or in a partially or completely neutralized form, i.e., as a salt.
  • the cation is not particularly limited and may be selected from the group consisting of alkali metals, such as sodium or potassium, and ammonium cations.
  • the polymeric polycarboxylic acid or salt thereof is selected from the group consisting of homopolymers and copolymers of ⁇ , ⁇ -ethylenically unsaturated carboxylic acids; and copolymers of at least one ⁇ , ⁇ -ethylenically unsaturated carboxylic acid and at least one sulfo group containing monomer.
  • Suitable ⁇ , ⁇ -ethylenically unsaturated carboxylic acids include acrylic acid, methacrylic acid and polymaleic acid.
  • Suitable sulfo group containing monomers include 2-propene-1-sulfonic acid (allylsulfonic acid), 2-methyl-2-propene-1-sulfonic acid (methallylsulfonic acid), vinylsulfonic acid, styrenesulfonic acids, i.e.2-styrenesulfonic acid, 3-styrenesulfonic acid and 4-styrenesulfonic acid, and 2-acrylamido-2-methylpropane sulfonic acid (AMPS).
  • allylsulfonic acid 2-methyl-2-propene-1-sulfonic acid
  • methallylsulfonic acid vinylsulfonic acid
  • styrenesulfonic acids i.e.2-styrenesulfonic acid, 3-styrenesulfonic acid and 4-styrenesulfonic acid
  • AMPS 2-acrylamido-2-methylpropane sulfonic acid
  • the polymeric polycarboxylic acid is a homopolymer of acrylic acid, a homopolymer of methacrylic acid, a copolymer of acrylic acid and maleic acid, or a copolymer of methacrylic acid and maleic acid, most preferably a homopolymer of acrylic acid.
  • suitable polymeric components are commercially available from BASF SE under the trade name SOKALAN®, such as SOKALAN® PA 20, SOKALAN® PA 15, SOKALAN® CP 10S, SOKALAN® PA 25 CL PN, SOKALAN® CP 12S, SOKALAN® PA 40.
  • SOKALAN® such as SOKALAN® PA 20, SOKALAN® PA 15, SOKALAN® CP 10S, SOKALAN® PA 25 CL PN, SOKALAN® CP 12S, SOKALAN® PA 40.
  • “CP” generally designates a copolymer
  • PA” generally designates a polyacrylate.
  • the amount of polymeric polycarboxylic acid or salt thereof, if present, may be in the range of from 0.01 to 2 wt.-%, preferably 0.2-1.2 wt.-%, more preferably 0.2-0.6 wt.-%, relative to the amount of cementitious binder.
  • the set control agent is present in the mixing water and/or the dry mix. In a practical embodiment, the set control agent is dissolved in a part of the mixing water, and the dry mix, comprising the cementitious binder, optionally an extraneous aluminate source, and optionally an extraneous sulfate source, is added to the mixture. The remainder of the water is then added to adjust consistency.
  • the set control agent is incorporated to the dry mix before the addition of mixing water.
  • Accelerator Agent In a preferred embodiment, an accelerator agent solution comprising at least one agent selected from the group consisting of an aluminum ion source, an aluminate source and a silicate source is incorporated into the cementitious slurry. Addition of the accelerator agent solution may occur before the foaming of the cementitious slurry or substantially concurrent with the foaming of the cementitious slurry or timely overlapping with the foaming of the cementitious slurry.
  • the invention also envisages the use of combinations of accelerator agents, for example the combination of an aluminum ion source and a silicate source.
  • the dosage of the individual accelerator agents into the cementitious slurry preferably occurs temporally or spatially separated.
  • introduction of the accelerator agents into the cementitious slurry can occur by dosing devices at different positions of the tubing or hose lines.
  • a stream of the cementitious slurry can be divided into partial streams, an accelerator can be added to each partial stream, and the partial streams can be combined again.
  • the accelerator agent acts to induce the production of ettringite, a highly hydrated sulfoaluminate crystalline phase containing several water molecules in its structural unit.
  • the accelerator agent is water soluble.
  • Water soluble for the purpose of the present invention means that the solubility of an agent in water at 25°C and atmospheric pressure is 0.1 g L -1 or more, preferably 1 g L -1 or more, or more preferred 100 g L -1 or more.
  • the accelerator agent solution comprises an aluminum ion source.
  • the aluminum ion source is selected from the group consisting of aluminum salts, aluminum complexes, and mixtures thereof, preferably aluminum sulfate.
  • the source of aluminum ions may include alkali-free accelerators based on aluminum compounds, e.g., aluminum salts such as sulfates, nitrates, fluorides and/or their hydrates; aluminum oxides; and aluminum hydroxides.
  • the source of aluminum ions may be selected from the group consisting of aluminum salts, aluminum complexes, and mixtures thereof.
  • the source of aluminum ions is selected from the group consisting of aluminum salts, especially aluminum sulfates.
  • the amount of the source of aluminum ions in the setting accelerator agent is in the range of from 0.0005 to 0.05 mol, more preferably 0.004 to 0.012 mol, per 100 g of cementitious binder.
  • the amount of sulfate in the source of aluminum ions is in the range of from 0.0008 to 0.075 mol, more preferably 0.006 to 0.02 mol, per 100 g of cementitious binder.
  • the accelerator agent may contain additives to provide shelf stability and other desirable properties to the accelerator agent. Formulations of the accelerator agents may be stabilized by various chemicals.
  • Such stabilizers include organic acids such as carboxylic acids, dicarboxylic acids, hydroxycarboxylic acids, aminocarboxylic acids, phosphoric acid, phosphorous acid, phosphonic acids, sulfamic acid; inorganic acids such as sulfuric acid, nitrous acid, phosphoric acid, phosphorous acid, hydrofluoric acid, hexafluorosilicic acid, and mixtures thereof; urea; polymeric stabilizers, such as polyacrylamides, polycarboxylates, polysulfonates, and copolymers and mixtures thereof; aluminosilicates such as attapulgite, sepiolite and bentonite; and colloidal silica.
  • organic acids such as carboxylic acids, dicarboxylic acids, hydroxycarboxylic acids, aminocarboxylic acids, phosphoric acid, phosphorous acid, phosphonic acids, sulfamic acid
  • inorganic acids such as sulfuric acid, nitrous acid,
  • setting accelerator agent may additionally comprise calcium and magnesium compounds such as for example sulfates, as well as amines, for example alkanolamines such as diethanolamine, triethanolamine, diisopropanolamine and triisopropanolamine and mixtures thereof.
  • a water-soluble magnesium salt may be contained in the aluminum ion source-based accelerator agent. Any such salt may be used, but the preferred salts are magnesium carbonate, or magnesium sulfate or mixtures of these salts. While the magnesium sulfate used in this invention may be any magnesium sulfate, the preferred magnesium is the hydrate MgSO 4 ⁇ 7H 2 O, known as Epsom Salts.
  • the accelerator agent solution comprises an aluminate source.
  • aluminate source alkali metal aluminates, such as sodium aluminate, are preferred.
  • the accelerator agent solution comprises a silicate source.
  • the silicate source may be selected from the group consisting of water-soluble alkali metal silicates and quaternary ammonium silicates.
  • a preferred silicate source is sodium silicate.
  • Alkali metal silicates are commercial available as waterglass. Waterglass can be obtained by the reaction of alkali metal carbonates with quartz sand (silicon dioxide). However, they can also be produced from mixtures of reactive silicas with the appropriate aqueous alkali metal hydroxides.
  • the alkali metal silicates of the following formula may be used: m SiO2 ⁇ n M2O, wherein M is an alkali metal, preferably Li, Na or K or a mixture thereof, and the alkali metal silicate has a molar ratio m:n (also termed "modulus") from 0.5 to 5, preferably from 1 to 4, more preferably from 1.7 to 3.3.
  • the waterglass is preferably a sodium waterglass, potassium waterglass or lithium waterglass and most preferably a sodium waterglass. However, it is also possible to use a mixture of the waterglasses mentioned.
  • Potassium waterglasses are mainly marketed as aqueous solutions because they are very hygroscopic; sodium waterglasses in the advantageous modulus range are also obtainable commercially as solids.
  • the solids contents of commercially available aqueous waterglass solutions are generally from 20 to 60 wt.-%, preferably from 40 to 60 wt.-%.
  • the silicate source can be a quaternary ammonium silicate, such as tetraalkyl ammonium silicate (including hydroxy- and alkoxy- containing alkyl groups generally of from 1 to 4 carbon atoms in the alkyl or alkoxy group).
  • the setting accelerator agent preferably comprises an aqueous solution of the silicate source.
  • the silicates form a number of structures in alkaline solution, including orthosilicate (SiO 4 4- ), pyrosilicate (Si2O7 6- ) and longer linear structures, and cyclic and branched structures, all of which are in dynamic equilibrium.
  • the amount of the silicate source introduced by the setting accelerator agent is in the range from 0.03 to 10 wt.-%, per 100 g of cementitious binder.
  • Foam-stabilizing agent The aqueous cementitious slurry comprises a foam-stabilizing agent.
  • the foam-stabilizing agent is selected from the group consisting of foam-stabilizing inorganic particles, surfactants, proteins and combinations thereof.
  • the foam-stabilizing agent is present in the mixing water and/or the dry mix together with the set control agent and the cementitious binder.
  • the term “foam-stabilizing particles” is known in the art and may refer to pickering particles.
  • Inorganic particles that have been subjected to pre-treatment with a surface modifier may be used, including inorganic particles that have been pre-treated with an amphiphile.
  • the foam-stabilizing inorganic particles are inorganic particles treated with an amphiphilic compound.
  • inorganic particles preferably refers to inorganic particles selected from the group consisting of: ⁇ Oxides, including pure and mixed metal oxides (particularly aluminum oxide, silicon dioxide, spinels, cerium-gadoliniumoxide, zirconium oxide, magnesium oxide, tin oxide, titanium oxide and cerium oxide); ⁇ Hydroxides (particularly aluminum hydroxide, calcium hydroxide, magnesium hydroxide, very particularly aluminum hydroxide); ⁇ Carbides (particularly silicon carbide, boron carbide); e Nitrides (particularly silicon nitride, boron nitride); ⁇ Phosphates (particularly calcium phosphates, such as tri-calciumphosphate, hydroxyapatite); ⁇ Carbonates (particularly nickel carbonate, calcium carbonate (ground limestone or precipitated calcium carbonate), magnesium carbonate); ⁇ Silicates (particularly silicon dioxide, silica fume, fly ash, quartz, ground glasses, slag, calcium silicates, mullite, cordierite, clay minerals like
  • the inorganic particles are selected from the group consisting of silica particles, alumina particles, zirconia particles, calcium carbonate particles and mixtures thereof.
  • the particle size of the inorganic particles may vary within a broad range.
  • suitable median particle sizes D 50 range from 30 nm to 300 ⁇ m, preferably from 100 nm to 250 ⁇ m, more preferably from 100 nm to 150 ⁇ m, even more preferably from 100 nm to 100 ⁇ m.
  • suitable particle sizes range from 100 nm to 10 ⁇ m, preferably 100 nm to 2 ⁇ m. It was found that the particle size distribution is of less importance. Good foams can be obtained with narrow as well as with broad particle size distributions.
  • the at least one group of inorganic particles has a median particle size D 50 measured by dynamic light scattering in the range of from 30 nm to 300 ⁇ m.
  • Dx particle size
  • the term “particle size (Dx)” refers to the diameter of a particle distribution, wherein x % of the particles have a smaller diameter.
  • the D50 particle size is thus the median particle size.
  • the Dx particle size can e.g. be measured by laser diffraction or dynamic light scattering (DLS) methods.
  • DLS dynamic light scattering
  • ISO 22412:2008 is preferably used.
  • Dynamic light scattering (DLS), sometimes referred to as Quasi-Elastic Light Scattering (QELS), is a non-invasive, well-established technique for measuring the size and size distribution of molecules and particles typically in the submicron region.
  • the particles were characterized, which have been dispersed in a liquid, preferably water or ethanol.
  • the Brownian motion of particles or molecules in suspension causes laser light to be scattered at different intensities. Analysis of these intensity fluctuations yields the velocity of the Brownian motion and hence the particle size using the Stokes-Einstein relationship.
  • the distribution can be a volume distribution (D v ), a surface distribution (D s ), or a number distribution (D n ).
  • the Dx value refers to a number distribution, wherein x(number) % of the particles have a smaller diameter.
  • amphiphilic compound is known in the art and relates to organic compounds having an apolar part (also identified as tail or group R) and a polar part (also identified as head group). Accordingly, suitable amphiphilic molecules contain a tail coupled to a head group, typically by covalent bonds. Such amphiphilic molecules typically contain one tail and one head group, but may also contain more than one head group.
  • the tail can be aliphatic (linear or branched) or cyclic (alicyclic or aromatic) and can carry substituents. Such substituents are e.g.
  • tails are optionally substituted linear carbon chains of 2 to 8 carbon atoms, more preferably linear carbon chains of 3 to 8, 4 to 8 or 5 to 8 carbon atoms.
  • “secondary -OH” and “secondary -NH 2 " shall mean that the resulting substituted tail group constitutes a secondary alcohol or a secondary amine.
  • the head groups that are coupled to the tail preferably are ionic groups, ionizable groups and/or polar groups. Examples of possible head groups and corresponding salts are specified in Table 1 below (wherein the tail is designated as R).
  • Carboxylic acids Preferred head groups are selected from the group consisting of carboxylic acid groups, gallates, amines and sulfonates. Particularly preferred head groups are selected from the group consisting of carboxylic acid groups (i.e. -C(O)OH groups), gallates and amine groups where X preferably represents H or methyl.
  • a preferred carboxylic acid is enanthic acid (heptanoic acid).
  • a preferred gallate is butyl gallate.
  • a preferred amine is heptylamine.
  • Carboxylic acid groups are most preferred. The amphiphilic molecules reduce the surface tension of an air-water interface to values lower than or equal to 65 mN/m for concentrations lower than or equal to 0.5 mol/l.
  • amphiphilic molecules have a critical micelle concentration (CMC) higher than 10 ⁇ mol/l and/or they have a solubility higher than 1 ⁇ mol/I.
  • the amphiphilic compound comprises at least one polar head group and at least one apolar tail group, wherein the at least one head group is selected from the group consisting of phosphates, phophonates, sulfates, sulfonates, alcohols, amines, amides, pyrrolidines, gallates, and carboxylic acids; and wherein the at least one tail group is selected from the group consisting of an aliphatic or an aromatic or a cyclic group with 2 to 8 carbon atoms, wherein the carbon atoms are optionally substituted with one or more, same or different substituents selected from the group consisting of C 1 -C 6 -alkyl, secondary -OH, and secondary –NH 2 .
  • CMC critical micelle concentration
  • the amphiphilic compound comprises at least one head group selected from the group consisting of a carboxylic group, a 3,4,5-trihydroxybenzoyloxy group and an amino group, and at least one tail group selected from aliphatic groups with 2 to 8 carbon atoms.
  • hydrophobized inorganic particles relates to inorganic particles, wherein the particle’s surface is modified with amphiphilic molecules, so as to reduce the hydrophilic properties of the inorganic particle. Surface modification in this context means that the amphiphilic compounds are adsorbed on the particle’s surface.
  • the amount of amphiphilic compound per inorganic particle BET surface is from 0.5 to 160 ⁇ mol/m 2 , preferably from 10 to 140 ⁇ mol/m 2 , more preferably from 20 to 120 ⁇ mol/m 2 .
  • the multi point BET method may include introducing a suitable amount of the inorganic particles into a BET tube, and then degassing the sample using flowing nitrogen at a temperature of 60°C for a period of time from about 5.0 hours prior to analysis.
  • the multi point surface area may be determined using nitrogen as the adsorbate gas at 77.350 Kelvin.
  • a cross-sectional area of the nitrogen adsorbate of 16.200 square angstroms may be used to calculate surface area.
  • surfactants may be used as foam-stabilizing agent.
  • Surfactants include non-ionic surfactants, anionic surfactants, cationic surfactants, zwitterionic surfactants.
  • Non-ionic surfactants include fatty alcohols, cetyl alcohol, stearyl alcohol, and cetostearyl alcohol (comprising predominantly cetyl and stearyl alcohols), and oleyl alcohol.
  • polyethylene glycol alkyl ethers (Brij) CH3-(CH2)10- 16 -(O-C 2 H 4 ) 1-25 -OH such as octaethylene glycol monododecyl ether or pentaethylene glycol monododecyl ether; polypropylene glycol alkyl ethers CH3-(CH2)10-16-(O- C 3 H 6 ) 1-25 -OH; glucoside alkyl ethers CH3-(CH2)10-16-(O-glucoside)1-3-OH such as decyl glucoside, lauryl glucoside, octyl glucoside; polyethylene glycol octylphenyl ethers C 8 H 17 -(C 6 H 4 )-(O-C 2 H 4 ) 1-25 -OH such as Triton X-100; polyethylene glycol alkylphenyl ethers C9H19-(C6H4)-(O-C) 1
  • Preferred non-ionic surfactants also include alkyl polyglucosides.
  • Anionic surfactants contain anionic functional groups at their head, such as sulfate, sulfonate, phosphate, and carboxylates.
  • Prominent alkyl sulfates include ammonium lauryl sulfate, sodium lauryl sulfate (sodium dodecyl sulfate, SLS, or SDS), and the related alkyl-ether sulfates sodium laureth sulfate (sodium lauryl ether sulfate or SLES), and sodium myreth sulfate.
  • Others include docusate (dioctyl sodium sulfosuccinate), perfluorooctanesulfonate (PFOS), perfluorobutanesulfonate, alkyl- aryl ether phosphates, alkyl ether phosphates.
  • Preferred carboxylates include the alkyl carboxylates, such as sodium stearate. More specialized species include sodium lauroyl sarcosinate and carboxylate-based fluorosurfactants such as perfluorononanoate, perfluorooctanoate (PFOA or PFO).
  • Cationic surfactants include, dependent on the pH, primary, secondary, or tertiary amines: Primary and secondary amines become positively charged at a pH below 10. An example is octenidine dihydrochloride.
  • cationic surfactants include permanently charged quaternary ammonium salts, such as cetrimonium bromide (CTAB), cetylpyridinium chloride (CPC), benzalkonium chloride (BAC), benzethonium chloride (BZT), dimethyldioctadecylammonium chloride, dioctadecyldimethylammonium bromide (DODAB).
  • CTC cetrimonium bromide
  • CPC cetylpyridinium chloride
  • BAC benzalkonium chloride
  • BZT benzethonium chloride
  • dimethyldioctadecylammonium chloride dioctadecyldimethylammonium bromide
  • DODAB dioctadecyldimethylammonium bromide
  • Zwitterionic (amphoteric) surfactants have both cationic and anionic centers attached to the same molecule.
  • the anionic part can be more variable and include sulfonates, as in the sultaines CHAPS (3-[(3- Cholamidopropyl)dimethylammonio]-1-propanesulfonate) and cocamidopropyl hydroxysultaine.
  • Betaines such as cocamidopropyl betaine have a carboxylate with the ammonium.
  • the most common biological zwitterionic surfactants have a phosphate anion with an amine or ammonium, such as the phospholipids phosphatidylserine, phosphatidylethanolamine, phosphatidylcholine, and sphingomyelins. The proportion of the surfactant can vary over a broad range.
  • the surfactant may be present in an amount of up to 5 wt.-%, preferably up to 1.5 wt.-%.
  • proteins may be used as foam-stabilizing agent.
  • proteins are proteins of animal origin, such as bovine serum albumin, egg ovalbumin, milk caseins, beta-lactoglobulin or keratin, or proteins of plant origin, such as soy-based protein.
  • a protein with a molecular weight of 1,000 to 50,000 Daltons may suitably be used.
  • Polyol As an optional ingredient, the method of the invention may involve a polyol.
  • at least one of the set control agent and the acceleration agent comprises a polyol.
  • the polyol is employed in an amount of 0.05 to 2.5 wt.-%, preferably 0.15 to 0.5 wt.-%, relative to the amount of cementitious binder. It is believed that polyols such as glycerol chelate calcium ions of e.g. calcium sulfate or C3A. As a result, calcium ion dissociation is accelerated. Chelation of calcium ions also stabilizes calcium in solution and accelerates the dissolution of calcium aluminate phases, thereby rendering aluminate from these calcium aluminate phases more accessible. “Polyol” is intended to denote a compound having at least two alcoholic hydroxyl groups in its molecule.
  • Useful polyols have at least 3 alcoholic hydroxyl groups in its molecule, for example 3, 4, 5 or 6 alcoholic hydroxyl groups. Polyols having vicinal hydroxyl groups are preferred. Polyols having at least three hydroxyl groups bound to three carbon atoms in sequence are most preferred. The ability of the polyol to chelate calcium ions and thereby stabilize calcium in solution can be assessed by a calcium aluminate precipitation test.
  • the polyol in a calcium aluminate precipitation test in which a test solution, obtained by supplementing 400 mL of a 1 wt.-% aqueous solution of the polyol with 20 mL of a 1 mol/L NaOH aqueous solution and 50 mL of a 25 mmol/L NaAlO 2 aqueous solution, is titrated with a 0.5 mol/L CaCl 2 aqueous solution at 20°C, inhibits precipitation of calcium aluminate up to a calcium concentration of 75 ppm, preferably 90 ppm.
  • the test detects the precipitation of calcium aluminate by turbidity. Initially, the test solution is a clear solution.
  • the clear test solution is titrated with a CaCl 2 aqueous solution at a constant dosage rate of, e.g., 2 mL/min, as described above.
  • a CaCl 2 aqueous solution at a constant dosage rate of, e.g., 2 mL/min, as described above.
  • the titration endpoint expressed as the maximum calcium concentration (as Ca 2+ ), before the onset of turbidity can be calculated from the elapsed time to the onset point.
  • the polyol is selected from the group consisting of compounds consisting of carbon, hydrogen, and oxygen only and does not contain a carboxyl group (COOH) in its molecule.
  • the polyol is selected from the group consisting of monosaccharides, oligosaccharides, water-soluble polysaccharides, compounds of general formula (P-I) or dimers or trimers of compounds of general formula (P-I): (P-I) wherein X is wherein R is –CH 2 OH, –NH 2 , n is an integer from 1 to 4, m is an integer from 1 to 8.
  • the polyol is selected from saccharides.
  • Useful saccharides include monosaccharides, such as glucose and fructose; disaccharides, such as lactose and sucrose; trisaccharides, such as raffinose; and water-soluble polysaccharides, such as amylose and maltodextrins.
  • sugar alcohols are organic compounds, typically derived from sugars, containing one hydroxyl group (–OH) attached to each carbon atom.
  • Useful sugar alcohols are mannitol, sorbitol, xylitol, arabitol, erythritol and glycerol. Among these, glycerol is particularly preferred. It is envisaged that carbonates of polyhydric alcohols such as glycerol carbonate can act as a polyol source.
  • Compounds of formula (P-I) wherein X is (P-Ib) include pentaerythritol, and tris(hydroxymethyl)aminomethane.
  • Compounds of formula (P-I) wherein X is (P-Ic) include triethanolamine.
  • Dimers or trimers denote compounds wherein two or three molecules of general formula (P-I) are linked via an ether bridge and which are formally derived from a condensation reaction with elimination of one or two molecules of water. Examples of dimers and trimers of compounds of formula (P-I) include dipentaerythritol and tripentaerythritol.
  • the primary compounds are represented in the cement notation by the oxide varieties: C for CaO, M for MgO, S for SiO2, A for Al2O3, $ for SO3, F for Fe2O3, and H for H2O.
  • the calcium silicate mineral phases are selected from the group consisting of C3S (alite) and C2S (belite).
  • the calcium silicate mineral phases provide primarily final strength properties.
  • the calcium aluminate mineral phases are selected from the group consisting of C3A, C4AF and C12A7, in particular C3A and C4AF.
  • the cementitious binder comprises a Portland cement clinker-based binder.
  • the term "Portland cement clinker-based binder” denotes any cement compound containing Portland clinker, especially CEM I within the meaning of standard EN 197-1, paragraph 5.2.
  • a preferred cement is ordinary Portland cement (OPC) according to DIN EN 197-1.
  • the phases constituting Portland cement mainly are alite (C3S), belite (C2S), calcium aluminate (C3A), calcium ferroaluminate (C4AF) and other minor phases.
  • Commercially available OPC may either contain calcium sulfate ( ⁇ 7 wt.-%) or is essentially free of calcium sulfate ( ⁇ 1 wt.-%).
  • the cementitious binder is controlled for its content of available aluminate, calculated as Al(OH) 4 – .
  • available aluminate calculated as Al(OH) 4 – .
  • approximate proportions of the main minerals in Portland cement are calculated by the Bogue formula which in turn is based on the elemental composition of the clinker determined, e.g., by means of X-ray fluorescence (XRF).
  • XRF X-ray fluorescence
  • “Available aluminate” is meant to encompass mineral phases and Al-containing compounds that are capable of generating Al(OH) 4 – in alkaline aqueous environments.
  • Calcium aluminate phases such as C3A (Ca3Al2O6), dissolve in an alkaline aqueous environment to yield Al(OH) 4 – and Ca 2+ ions.
  • the concentration of mineral phases and Al-containing compounds that are capable of generating Al(OH)4 – is expressed as mol of Al(OH) 4 – per 100 g of cementitious binder. It is believed that the common calcium aluminate mineral phases – in contrast to crystalline aluminum oxides – are sources of available aluminate.
  • the amount of available aluminate in a given cementitious binder may be determined by methods capable of discriminating between the mineral phases constituting the cementitious binder.
  • a useful method for this purpose is Rietveld refinement of an X- ray diffraction (XRD) powder pattern. This software technique is used to refine a variety of parameters, including lattice parameters, peak position, intensities and shape. This allows theoretical diffraction patterns to be calculated. As soon as the calculated diffraction pattern is almost identical to the data of an examined sample, precise quantitative information on the contained mineral phases can be determined.
  • XRD X- ray diffraction
  • calcium aluminate mineral phases capable of generating Al(OH)4 – in alkaline aqueous environments are tricalcium aluminate (C3A), monocalcium aluminate (CA), mayenite (C12A7), grossite (CA2), Q-phase (C20A13M3S3) or tetracalcium aluminoferrite (C4AF).
  • cementitious binder is Portland cement
  • the cementitious binder is Portland cement
  • the amount of available aluminate may be obtained by determining the total amount of Al from the elemental composition of the cementitious binder, e.g., by XRF, and subtracting therefrom the amount of crystalline aluminum compounds not capable of generating available aluminate, as determined by XRD and Rietveld refinement. This method also takes into account amorphous, soluble aluminum compounds capable of generating available aluminate.
  • Such crystalline aluminum compounds not capable of generating available aluminates include compounds of the melilite group, e.g., gehlenite (C2AS), compounds of the spinel group, e.g., spinel (MA), mullite (Al2Al2+2xSi2-2xO10-x), and corundum (Al2O3).
  • the invention makes use of cementitious binders containing 0.05 to 0.2 mol of available aluminate from calcium aluminate mineral phases, as determined by, e.g., XRD analysis.
  • the cementitious slurry contains an extraneous aluminate source.
  • the extraneous aluminate source provides available aluminate as defined above.
  • the extraneous aluminate source is a sparingly soluble aluminate source, e.g., having an aqueous solubility at 25°C and atmospheric pressure of 0.05 g L -1 or lower, preferably 0.005 g L -1 or lower.
  • the limited solubility of the extraneous aluminate source acts to avoid uncontrolled premature setting of cementitious slurry.
  • the extraneous aluminate source is contained in the cementitious slurry in an undissolved (e.g., powder) or only partially dissolved form.
  • the extraneous aluminate source is selected from the group consisting of non- calciferous aluminate sources, such as amorphous aluminum hydroxide; and calciferous aluminate sources such as high alumina cement, sulfoaluminate cement or synthetic calcium aluminate mineral phases.
  • amorphous aluminum hydroxide is used as the extraneous aluminate source.
  • High aluminate cement means a cement containing a high concentration of calcium aluminate phases, e.g., at least 30 wt.-%. More precisely, said mineralogical phase of aluminate type comprises tricalcium aluminate (C3A), monocalcium aluminate (CA), mayenite (C12A7), tetracalcium aluminoferrite (C4AF), or a combination of several of these phases.
  • Sulfoaluminate cement has a content of ye’elimite (of chemical formula 4CaO.3Al 2 O 3 .SO 3 or C4A3$ in cement notation) of typically greater than 15 wt.-%.
  • Suitable synthetic calcium aluminate mineral phases include amorphous mayenite (C12A7).
  • the cementitious slurry contains 0.02 to 0.20 mol of total available aluminate, calculated as Al(OH)4 – , from the calcium aluminate mineral phases plus the optional extraneous aluminate source, per 100 g of cementitious binder.
  • the cementitious slurry contains at least 0.065 mol, in particular at least 0.072 mol, of total available aluminate, per 100 g of cementitious binder It has been found that cementitious slurries containing at least 0.05 mol of total available aluminate per 100 g of cementitious binder exhibit optimum performance regarding open time before setting and early strength development. Otherwise, if the cementitious binder contains more than 0.2 mol of total available aluminate per 100 g of cementitious binder, open time is shorter as early strength development is too fast.
  • the cementitious slurry additionally comprises an extraneous sulfate source, preferably a sulfate source selected from the group consisting of gypsum, hemihydrate, anhydrite and mixtures thereof.
  • an extraneous sulfate source preferably a sulfate source selected from the group consisting of gypsum, hemihydrate, anhydrite and mixtures thereof.
  • the molar ratio of total available aluminate to sulfate is 0.4 to 3.5.
  • the sulfate source is a compound capable of providing sulfate ions in an alkaline aqueous environment.
  • the sulfate source has an aqueous solubility at a temperature of 30°C to provide a sulfate ion concentration of at least 0.6 mmol g ⁇ L -1 .
  • the aqueous solubility of the sulfate source is suitably determined in water with a starting pH value of 7.
  • the molar ratio of total available aluminate to sulfate is in the range of 0.4 to 3.5, preferably 0.57 to 0.8, in particular about 0.67.
  • Portland cement in its commercially available form typically contains small amounts of a sulfate source. If the intrinsic amount of sulfate is unknown, it can be determined by methods familiar to the skilled person such as elemental analysis by XRF.
  • a sulfate source commonly used in the cement production alkaline earth metal sulfates, alkali metal sulfates, or mixed forms thereof, such as gypsum, hemihydrate, anhydrite, arkanite, thenardite, syngenite, langbeinite, are typically crystalline, the amount thereof can also be determined by XRD.
  • the extraneous sulfate source may be selected from the group consisting of calcium sulfate dihydrate, anhydrite, ⁇ - and ⁇ -hemihydrate, i.e. ⁇ -bassanite and ⁇ - bassanite, or mixtures thereof.
  • the calcium sulfate source is ⁇ -bassanite and/or ⁇ -bassanite.
  • the sulfate source is not especially limited, other possible sulfate sources are for example alkali metal sulfates like potassium sulfate or sodium sulfate. It is envisaged that an additive can act as a source of both aluminate and sulfate, such as aluminum sulfate hexadecahydrate or aluminum sulfate octadecahydrate. Preferably, the sulfate source is a calcium sulfate source.
  • the mineral foam comprises sulfate, inclusive of the intrinsic SO4 content of the binder and any added extraneous sulfate source, in an amount in the range of from 0.025 to 0.5 mol, per 100 g of cementitious binder.
  • Supplementary Cementitious Materials the mineral foam additionally comprises at least one of a latent hydraulic binder, a pozzolanic binder and a filler material.
  • a “latent hydraulic binder” is preferably a binder in which the molar ratio (CaO + MgO):SiO2 is from 0.8 to 2.5 and particularly from 1.0 to 2.0.
  • the above-mentioned latent hydraulic binders can be selected from the group consisting of industrial and/or synthetic slag, in particular from blast furnace slag, electrothermal phosphorous slag, steel slag and mixtures thereof.
  • the “pozzolanic binders” can generally be selected from the group consisting of amorphous silica, preferably precipitated silica, fumed silica and microsilica, ground glass, metakaolin, aluminosilicates, fly ash, preferably brown-coal fly ash and hard-coal fly ash, natural pozzolans such as tuff, trass and volcanic ash, calcined clays, burnt shale, rice husk ash, natural and synthetic zeolites and mixtures thereof.
  • the slag can be either industrial slag, i.e. waste products from industrial processes, or else synthetic slag. The latter can be advantageous because industrial slag is not always available in consistent quantity and quality.
  • Blast furnace slag (BFS) is a waste product of the glass furnace process.
  • Other materials are granulated blast furnace slag (GBFS) and ground granulated blast furnace slag (GGBFS), which is granulated blast furnace slag that has been finely pulverized.
  • Ground granulated blast furnace slag varies in terms of grinding fineness and grain size distribution, which depend on origin and treatment method, and grinding fineness influences reactivity here.
  • the Blaine value is used as parameter for grinding fineness, and typically has an order of magnitude of from 200 to 1000 m 2 kg -1 , preferably from 300 to 500 m 2 kg -1 . Finer milling gives higher reactivity.
  • the expression “blast furnace slag” is however intended to comprise materials resulting from all of the levels of treatment, milling, and quality mentioned (i.e. BFS, GBFS and GGBFS).
  • Blast furnace slag generally comprises from 30 to 45% by weight of CaO, about 4 to 17% by weight of MgO, about 30 to 45% by weight of SiO2 and about 5 to 15% by weight of Al 2 O 3 , typically about 40% by weight of CaO, about 10% by weight of MgO, about 35% by weight of SiO2 and about 12% by weight of Al2O3.
  • Electrothermal phosphorous slag is a waste product of electrothermal phosphorous production.
  • Amorphous silica is preferably an X ray-amorphous silica, i.e. a silica for which the powder diffraction method reveals no crystallinity.
  • the content of SiO2 in the amorphous silica is advantageously at least 80% by weight, preferably at least 90% by weight.
  • Precipitated silica is obtained on an industrial scale by way of precipitating processes starting from water glass. Precipitated silica from some production processes is also called silica gel. Fumed silica is produced via reaction of chlorosilanes, for example silicon tetrachloride, in a hydrogen/oxygen flame. Fumed silica is an amorphous SiO2 powder of particle diameter from 5 to 50 nm with specific surface area of from 50 to 600 m 2 /g. Microsilica is a by-product of silicon production or ferrosilicon production, and likewise consists mostly of amorphous SiO2 powder. The particles have diameters of the order of magnitude of 0.1 ⁇ m.
  • Metakaolin is produced when kaolin is dehydrated. Whereas at from 100 to 200°C kaolin releases physically bound water, at from 500 to 800°C a dehydroxylation takes place, with collapse of the lattice structure and formation of metakaolin (Al2Si2O7). Accordingly, pure metakaolin comprises about 54% by weight of SiO2 and about 46% by weight of Al2O3. Fly ash is produced inter alia during the combustion of coal in power stations.
  • Class C fly ash (brown-coal fly ash) comprises according to WO 08/012438 about 10% by weight of CaO
  • class F fly ash (hard-coal fly ash) comprises less than 8% by weight, preferably less than 4% by weight, and typically about 2% by weight of CaO
  • the cementitious binder before being mixed with water in the presence of the set control agent, comprises less than 5 wt.-%, more preferably less than 3.5 wt.- %, most preferably less than 2 wt.-% of cementitious hydration products, relative to the total weight of the cementitious binder.
  • cementitious hydration products ettringite, portlandite, syngenite.
  • the presence and concentrations of these cementitious hydration products can be determined by Rietveld refinement of an X-ray diffraction (XRD) powder pattern.
  • XRD X-ray diffraction
  • the cementitious slurry additionally comprises a dispersant.
  • a water reducer in particular, a plasticizer or a super-plasticizer, preferably a plasticizer based on polyoxy polycarboxylate or phosphonates, is preferably added to the construction material before the conveying step.
  • a water reducer makes it possible to reduce the amount of mixing water for a given workability by typically 10-15%.
  • water reducers By way of example of water reducers, mention may be made of lignosulphonates, hydroxycarboxylic acids, carbohydrates, and other specific organic compounds, for example glycerol, polyvinyl alcohol, sodium alumino-methyl- siliconate and sulfanilic acid as described in the Concrete Admixtures Handbook, Properties Science and Technology, V.S. Ramachandran, Noyes Publications, 1984.
  • Super-plasticisers belong to a new class of water reducers and are capable of reducing water contents of mixing water, for a given workability, by approximately 30% by mass.
  • the PCP super-plasticisers may be noted.
  • PCP polyoxy polycarboxylate
  • PES polyoxy ethylene
  • a number of useful dispersants contain carboxyl groups, salts thereof or hydrolysable groups releasing carboxyl groups upon hydrolysis.
  • the milliequivalent number of carboxyl groups contained in these dispersant is lower than 3.0 meq/g, assuming all the carboxyl groups to be in unneutralized form.
  • useful dispersants include ⁇ comb polymers having a carbon-containing backbone to which are attached pendant cement-anchoring groups and polyether side chains, ⁇ non-ionic comb polymers having a carbon-containing backbone to which are attached pendant hydrolysable groups and polyether side chains, the hydrolysable groups upon hydrolysis releasing cement-anchoring groups, ⁇ colloidally disperse preparations of polyvalent metal cations, such as Al 3+ , Fe 3+ or Fe 2+ , and a polymeric dispersant which comprises anionic and/or anionogenic groups and polyether side chains, and the polyvalent metal cation is present in a superstoichiometric quantity, calculated as cation equivalents, based on the sum of the anionic and anionogenic groups of the polymeric dispersant, ⁇ sulfonated melamine-formaldehyde condensates, ⁇ lignosulfonates, ⁇ sulfonated ketone-formaldehyde condens
  • the dispersant is present in a weight percentage of 0.005 to 1.0, preferably 0.05 to 0.5, more preferably 0.02 to 0.15, relative to the cementitious binder.
  • Comb polymers having a carbon-containing backbone to which are attached pendant cement-anchoring groups and polyether side chains are particularly preferred.
  • the cement-anchoring groups are anionic and/or anionogenic groups such as carboxylic groups, phosphonic or phosphoric acid groups or their anions.
  • Anionogenic groups are the acid groups present in the polymeric dispersant, which can be transformed to the respective anionic group under alkaline conditions.
  • the structural unit comprising anionic and/or anionogenic groups is one of the general formulae (Ia), (Ib), (Ic) and/or (Id):
  • R 1 is H, C1-C4 alkyl, preferably H or methyl
  • R 2 is OM, PO 3 M 2 , or O-PO 3 M 2 ; with the proviso that X is a chemical bond if R 2 is OM; wherein R 3 is H or C 1 -C 4 alkyl, preferably H or methyl; n is 0, 1, 2, 3 or 4; R 4 is PO 3 M 2 , or O-PO 3 M 2 ; wherein R 5 is H or C 1 -C 4 alkyl, preferably H; Z is O or NR 7 ; R 7 is H, (C n1 H 2n1 )-OH, (C n1 H 2n1 )-PO 3 M 2 , (C n1 H 2n1 )-
  • the structural unit comprising a polyether side chain is one of the general formulae (IIa), (IIb), (IIc) and/or (IId): wherein R 10 , R 11 and R 12 independently of one another are H or C 1 -C 4 alkyl, preferably H or methyl; Z 2 is O or S; E is C2-C6 alkylene, cyclohexylene, CH2-C6H10, 1,2-phenylene, 1,3-phenylene or 1,4-phenylene; G is O, NH or CO-NH; or E and G together are a chemical bond; A is C2-C5 alkylene or CH2CH(C6H5), preferably C2-C3 alkylene; n2 is 0, 1, 2, 3, 4 or 5; a is an integer from 2 to 350, preferably 10 to 150, more preferably 20 to 100; R 13 is H, an unbranched or branched C 1 -C 4 alkyl group, CO-NH 2 or COCH 3 ;
  • R 16 , R 17 and R 18 independently of one another are H or C 1 -C 4 alkyl, preferably H;
  • E 2 is C 2 -C 6 alkylene, cyclohexylene, CH 2 -C 6 H 10 , 1,2-phenylene, 1,3-phenylene, or 1,4-phenylene, or is a chemical bond;
  • A is C2-C5 alkylene or CH2CH(C6H5), preferably C2-C3 alkylene;
  • n2 is 0, 1, 2, 3, 4 or 5;
  • L is C 2 -C 5 alkylene or CH 2 CH(C 6 H 5 ), preferably C 2 -C 3 alkylene;
  • a is an integer from 2 to 350, preferably 10 to 150, more preferably 20 to 100;
  • d is an integer from 1 to 350, preferably 10 to 150, more preferably 20 to 100;
  • R 19 is H or C1-C4 alkyl; and
  • R 20 is H or C1-C4 alkyl
  • the molar ratio of structural units (I) to structural units (II) varies from 1:3 to about 10:1, preferably 1:1 to 10:1, more preferably 3:1 to 6:1.
  • the polymeric dispersants comprising structural units (I) and (II) can be prepared by conventional methods, for example by free radical polymerization or controlled radical polymerization. The preparation of the dispersants is, for example, described in EP 0894811, EP 1851256, EP 2463314, and EP 0753488. More preferably, the dispersant is selected from the group of polycarboxylate ethers (PCEs). In PCEs, the anionic groups are carboxylic groups and/or carboxylate groups.
  • PCEs polycarboxylate ethers
  • the PCE is preferably obtainable by radical copolymerization of a polyether macromonomer and a monomer comprising anionic and/or anionogenic groups.
  • at least 45 mol-%, preferably at least 80 mol-% of all structural units constituting the copolymer are structural units of the polyether macromonomer or the monomer comprising anionic and/or anionogenic groups.
  • a further class of suitable comb polymers having a carbon-containing backbone to which are attached pendant cement-anchoring groups and polyether side chains comprise structural units (III) and (IV):
  • T is phenyl, naphthyl or heteroaryl having 5 to 10 ring atoms, of which 1 or 2 atoms are heteroatoms selected from the group consisting of N, O and S;
  • n3 is 1 or 2;
  • B is N, NH or O, with the proviso that n3 is 2 if B is N and n3 is 1 if B is NH or O;
  • A is C2-C5 alkylene or CH2CH(C6H5), preferably C2-C3 alkylene;
  • a2 is an integer from 1 to 300;
  • R 26 is H, C 1 -C 10 alkyl, C 5 -C 8 cycloalkyl, aryl, or heteroaryl having 5 to 10 ring atoms, of which 1 or 2 atoms are heteroatoms selected from the group consisting of N, O and S;
  • the structural unit (IV) is selected from the group consisting of the structural units (IVa) and (IVb): wherein D is
  • Polymers comprising structural units (III) and (IV) are obtainable by polycondensation of an aromatic or heteroaromatic compound having a polyoxyalkylene group attached to the aromatic or heteroaromatic core, an aromatic compound having a carboxylic, sulfonic or phosphate moiety, and an aldehyde compound such as formaldehyde.
  • the dispersant is a non-ionic comb polymer having a carbon- containing backbone to which are attached pendant hydrolysable groups and polyether side chains, the hydrolysable groups upon hydrolysis releasing cement-anchoring groups.
  • the structural unit comprising a polyether side chain is one of the general formulae (IIa), (IIb), (IIc) and/or (IId) discussed above.
  • the structural unit having pendant hydrolysable groups is preferably derived from acrylic acid ester monomers, more preferably hydroxyalkyl acrylic monoesters and/or hydroxyalkyl diesters, most preferably hydroxypropyl acrylate and/or hydroxyethyl acrylate.
  • the ester functionality will hydrolyze to (deprotonated) acid groups upon exposure to water at preferably alkaline pH, which is provided by mixing the cementitious binder with water, and the resulting acid functional groups will then form complexes with the cement component.
  • the dispersant is selected from the group consisting of colloidally disperse preparations of polyvalent metal cations, such as Al 3+ , Fe 3+ or Fe 2+ , and a polymeric dispersant which comprises anionic and/or anionogenic groups and polyether side chains.
  • the polyvalent metal cation is present in a superstoichiometric quantity, calculated as cation equivalents, based on the sum of the anionic and anionogenic groups of the polymeric dispersant.
  • Such dispersants are described in further detail in WO 2014/013077 A1, which is incorporated by reference herein.
  • Suitable sulfonated melamine-formaldehyde condensates are of the kind frequently used as plasticizers for hydraulic binders (also referred to as MFS resins). Sulfonated melamine-formaldehyde condensates and their preparation are described in, for example, CA 2172004 A1, DE 4411797 A1, US 4,430,469, US 6,555,683 and CH 686186 and also in Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed., vol. A2, page 131, and Concrete Admixtures Handbook - Properties, Science and Technology, 2. Ed., pages 411, 412.
  • Preferred sulfonated melamine-formaldehyde condensates encompass (greatly simplified and idealized) units of the formula in which n4 stands generally for 10 to 300.
  • the molar weight is situated preferably in the range from 2500 to 80000.
  • urea is particularly suitable to the sulfonated melamine units.
  • further aromatic units as well may be incorporated by condensation, such as gallic acid, aminobenzenesulfonic acid, sulfanilic acid, phenolsulfonic acid, aniline, ammoniobenzoic acid, dialkoxybenzenesulfonic acid, dialkoxybenzoic acid, pyridine, pyridinemonosulfonic acid, pyridinedisulfonic acid, pyridinecarboxylic acid and pyridinedicarboxylic acid.
  • An example of melaminesulfonate-formaldehyde condensates are the Melment® products distributed by Master Builders Solutions GmbH. Suitable lignosulfonates are products which are obtained as by-products in the paper industry.
  • Lignosulfonates have molar weights of between 2000 and 100000 g/mol. In general, they are present in the form of their sodium, calcium and/or magnesium salts.
  • suitable lignosulfonates are the Borresperse products distributed by Borregaard LignoTech, Norway.
  • Suitable sulfonated ketone-formaldehyde condensates are products incorporating a monoketone or diketone as ketone component, preferably acetone, butanone, pentanone, hexanone or cyclohexanone.
  • Condensates of this kind are known and are described in WO 2009/103579, for example. Sulfonated acetone-formaldehyde condensates are preferred. They generally comprise units of the formula (according to J. Plank et al., J. Appl. Poly. Sci.2009, 2018-2024): where m2 and n5 are generally each 10 to 250, M 2 is an alkali metal ion, such as Na + , and the ratio m2:n5 is in general in the range from about 3:1 to about 1:3, more particularly about 1.2:1 to 1:1.2.
  • aromatic units it is also possible for other aromatic units to be incorporated by condensation, such as gallic acid, aminobenzenesulfonic acid, sulfanilic acid, phenolsulfonic acid, aniline, ammoniobenzoic acid, dialkoxybenzenesulfonic acid, dialkoxybenzoic acid, pyridine, pyridinemonosulfonic acid, pyridinedisulfonic acid, pyridinecarboxylic acid and pyridinedicarboxylic acid.
  • suitable sulfonated acetone-formaldehyde condensates are the Melcret K1L products distributed by Master Builders Solutions GmbH.
  • Suitable sulfonated naphthalene-formaldehyde condensates are products obtained by sulfonation of naphthalene and subsequent polycondensation with formaldehyde. They are described in references including Concrete Admixtures Handbook - Properties, Science and Technology, 2. Ed., pages 411 -413 and in Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed., vol. A8, pages 587, 588. They comprise units of the formula Typically, molar weights (Mw) of between 1,000 and 50,000 g/mol are obtained.
  • Mw molar weights
  • aromatic units it is also possible for other aromatic units to be incorporated by condensation, such as gallic acid, aminobenzenesulfonic acid, sulfanilic acid, phenolsulfonic acid, aniline, ammoniobenzoic acid, dialkoxybenzenesulfonic acid, dialkoxybenzoic acid, pyridine, pyridinemonosulfonic acid, pyridinedisulfonic acid, pyridinecarboxylic acid and pyridinedicarboxylic acid.
  • suitable sulfonated ⁇ -naphthalene-formaldehyde condensates are the Melcret 500 L products distributed by Master Builders Solutions GmbH.
  • phosphonate containing dispersants incorporate phosphonate groups and polyether side groups.
  • Suitable phosphonate containing dispersants are those according to the following formula R-(OA 2 )n6-N-[CH2-PO(OM 3 2)2]2 wherein R is H or a hydrocarbon residue, preferably a C1-C15 alkyl radical, A 2 is independently C 2 -C 18 alkylene, preferably ethylene and/or propylene, most preferably ethylene, n6 is an integer from 5 to 500, preferably 10 to 200, most preferably 10 to 100, and M 3 is H, an alkali metal, 1/2 alkaline earth metal and/or an amine. Foaming The cementitious slurry is foamed.
  • Foaming means the injection of an inert gas into the slurry or the generation of an inert gas within the slurry to create a ternary system, wherein one phase is gaseous, one phase is liquid, and one phase is solid.
  • the gaseous phase is present as fine gas bubbles separated by cell walls obtained from the liquid and solid phases.
  • the cell walls meet each other at edges, which meet each other at nodes, thereby forming a framework.
  • the content of the gaseous phase in the inorganic foam may vary in a range of from 40 to 99%, preferably from 90 to 95% by volume.
  • the gas phase present in the foam can be introduced or generated by chemical foaming, mechanical foaming and combinations thereof.
  • blowing agents are peroxides, such as hydrogen peroxide, dibenzylperoxide, peroxobenzoic acid, peroxoacetic acid, alkali metal peroxides, perchloric acid, peroxomonosulfuric acid, dicumyl peroxide or cumyl hydroperoxide; isocyanates, carbonates and bicarbonates, such as CaCO 3 , Na 2 CO 3 , and NaHCO3, which are preferably used in combination with an acid, e.g., a mineral acid; metal powders, such as aluminum powder; azides, such as methyl azide; hydrazides, such as p-toluenesulfonylhydrazide; hydrazine.
  • peroxides such as hydrogen peroxide, dibenzylperoxide, peroxobenzoic acid, peroxoacetic acid, alkali metal peroxides, perchloric acid, peroxomonosulfuric acid, dicumyl peroxide
  • chemical foaming involves catalytic decomposition of a peroxide.
  • Suitable catalysts preferably comprise Mn 2+ , Mn 4+ , Mn 7+ or Fe 3+ cations.
  • the enzyme catalase may be used as catalyst.
  • suitable catalysts are MnO 2 and KMnO 4 .
  • Such catalysts are preferably used in combination with peroxide blowing agents. Further details regarding the components as used in the process for preparing a particle-stabilized inorganic foam based on a Portland cement clinker-based cementitious binder, to the inorganic foams thus obtained and to elements of construction comprising these inorganic foams are provided hereinafter.
  • the invention comprises casting the foamed or unfoamed cementitious slurry in a mould, foaming the unfoamed cementitious slurry, allowing the foamed cementitious slurry to set, and demoulding.
  • the invention comprises applying the foamed or unfoamed cementitious slurry onto a support and/or introducing the foamed or unfoamed cementitious slurry into a void space, foaming the unfoamed cementitious slurry, and allowing the foamed cementitious slurry to set.
  • the invention comprises a mineral foam obtainable by the method according to the invention for preparing a mineral foam.
  • the mineral foam according to the invention may have open cell or closed cell structure.
  • the invention comprises the use of the mineral foam according to the invention as a thermal insulator, acoustic insulator or acoustic absorber, for fire protection and/or as a construction material.
  • the mineral foam having open cell structure is used as an acoustic insulator or acoustic absorber whereas the mineral foam having closed cell structure is used as a thermal insulator, for fire protection and/or as a construction material.
  • the invention provides a method of manufacturing a building material comprising forming the mineral foam according to the invention into a material selected from the group consisting of a thermal insulator, an acoustic insulator, an acoustic absorber, a fire protection element and a construction material.
  • a material selected from the group consisting of a thermal insulator, an acoustic insulator, an acoustic absorber, a fire protection element and a construction material.
  • the initial setting time is defined as the time at which a paste or mortar deposited in the mold begins to oppose resistance to penetration by the Vicat needle.
  • the Vicat needle is allowed to fall by gravity.
  • Final setting is defined as having taken place when the Vicat needle, in contact with the upper side of the material, is not breaking its structure but only leaves the print of the pressure of the point of the needle.
  • Setting time for comparative samples is determined using a fully automated Vicat- measuring-system from DETTKI equipped with Vicat needle and two different loads (300 g and 1000 g). The measurement was conducted according to DIN EN 196-3.
  • Foam blocks were prepared by pouring a mix of suspension and hydrogen peroxide into a mold and letting the foam expand. After expansion (around 30 min), the foam surface was covered by a plastic wrap to prevent the surface from drying and cured for 24 h at room conditions. The following day, the plastic wrap was removed and the cured foam block demolded. After demolding, foam prisms (16/4/4 cm3) were cut from the foam block and after drying for 21 days after foaming at a temperature of 23°C and relative humidity of 50%, a hardened and dried foam prism was obtained. Dry density was measured by weighing the samples on a laboratory scale and dividing the weight by the volume.
  • Reference foam and two foam mixes comprising the set control/ accelerator combination were prepared as shown in table 2.
  • the Foaming Powder was first dispersed in water. Then, a dry mix of cement, sand, fly ash, microsilica, anhydrite, amorphous aluminum oxide and the solid constituents of the set control agent, i.e. sodium gluconate and potassium carbonate, were added and homogenized for 15 min.
  • the liquid components constitutes of the set control agent, i.e. Sokalan PA15 and Glycerin, were added to the suspension.15 seconds prior before mixing was ended, the acceleration agent, i.e. MasterRoc SA 160, was added. Foaming of the suspension was initiated by adding the hydrogen peroxide and mixing. The so obtained slurry was poured into a mold where the foam expansion evolved until the decomposition of the hydrogen peroxide was completed.
  • the acceleration agent i.e. MasterRoc SA 160
  • Example 2 demonstrates that it is possible to improve initial and final setting time by first adjusting the cement composition (if necessary) and using the set control and accelerator formulation.
  • Experiment 2 Two additional cements were tested to verify the compatibility of the set control- technology with different cement types. Because of a more favorable content of available aluminate, addition of Anhydrite and Amorphous Aluminum Oxide was not necessary. Preparation method was the same as in Experiment 1. The composition of the foams are shown in table 4. The initial setting time and the final setting time were determined using aliquots of the suspension taken prior to the addition of hydrogen peroxide. The density and compressive strength were measured of cured and dried foam samples after 21 days. The results are shown in table 5.
  • the initial setting time and the final setting time were determined using aliquots of the suspension taken prior to the addition of hydrogen peroxide.
  • the density and compressive strength were measured of cured and dried foam samples after 21 days. The results are shown in table 9. Open time was reduced significantly, so that mixing time had to be reduced from 15 down to 2 minutes.
  • Example 11 Open times and compressive strength with and without acceleration are in the same range as foams with glycerin (compare 11 versus 1, 12 versus 2 and 13 versus 10).
  • Example 11 was repeated with the use of citric acid (tricarboxylic acid) or tartaric acid (dicarboxylic acid) instead of sodium gluconate.
  • the following table 10a shows the respective foam compositions 11a and 11b.
  • Table 10a 11a* 11b* Milke CEM I 52.5 R [g] 500 500 Quartz Sand (0.1-0.3 mm) [g] 346.5 346.5 Fly Ash [g] 107.5 107.5 Micro Silica [g] 46 46 Foaming Powder [g] 47.87 47.87 (45.322 g CaCO3, 0.452g Nonanoic Acid 97%, 2.096g MnO2) Anhydrite [g] 50 50 Amorphous Aluminum Oxide [g] 12 12 Set control agent [g] 7.095 (4.504 g Sodium Carbonate; 0.255 g Sodium Citrate; 2.366 g Sokalan PA 15 [1] ) Set control agent [g] 7.095 (4.504 g Sodium Carbonate; 0.255 g Sodium tartrate; 2.366 g Sokalan PA 15 [1] ) Water [g] 562.68 562.68 Accelerator agent [g] - 78.36 (MasterRoc SA 160) Hydrogen Peroxide (30wt%) [g] 75.74 75.74 Ratio Water
  • compositions 11a and 11b were more inhomogeneities and less homogeneous cell structure as compared to the foam of composition 11.
  • compositions 11a and 11b rose significantly less than composition 11 during foaming (7 cm for 11a and 8.5 cm for 11b versus 13 cm for 11).
  • Table 12 14 Milke CEM I 52.5 R [g] 500 Quartz Sand (0.1-0.3 mm) [g] 346.5 Fly Ash [g] 107.5 Micro Silica [g] 46 Foaming Powder [g] - MnO 2 [g] 3.54 Surfactent (Vinapor GYP 2620) [g] 26.59 Anhydrite [g] 50 Amorphous Aluminum Oxide [g] 12 Set control agent [g] 7.095 (4.504 g Sodium Carbonate; 0.255 g Sodium Gluconate, 2.366 g Sokalan PA 15 [1] ) Water [g] 562.68 Accelerator agent [g] 78.36 (MasterRoc SA 160) Hydrogen Peroxide (30wt%) [g] 75.74 Ratio Water/binder 0.55 [1] polyacrylic acid, concentration 45 wt.-%

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

Un procédé de préparation d'une mousse minérale comprend les étapes consistant à : (a) fournir une suspension cimentaire aqueuse comprenant un liant cimentaire, un agent de stabilisation de mousse et un agent de régulation de durcissement ; et (b) faire mousser la suspension cimentaire ; l'agent de régulation de durcissement comprenant (i) un α-hydroxyacide monocarboxylique ou un sel de celui-ci et (ii) une source d'oxyanion choisie dans le groupe constitué par une source de borate et une source de carbonate. Un agent accélérateur choisi dans le groupe constitué par une source d'ions aluminium, une source d'aluminate et une source de silicate peut être ajouté à la suspension cimentaire. Le procédé permet l'utilisation de ciment Portland ordinaire ou de ciments d'argile calcinée calcaire sans compromettre la résistance finale de la mousse minérale.
EP24718060.7A 2023-03-28 2024-03-28 Mousse inorganique à base de ciment portland ordinaire Pending EP4688695A1 (fr)

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PCT/EP2024/058546 WO2024200688A1 (fr) 2023-03-28 2024-03-28 Mousse inorganique à base de ciment portland ordinaire

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CN120943604B (zh) * 2025-08-11 2026-02-27 旭辰矿业科技发展(徐州)有限公司 一种低温发泡的无机填充材料及其制备方法和应用
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Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3107852A1 (de) 1981-03-02 1982-09-16 Sika AG, vorm. Kaspar Winkler & Co., 8048 Zürich Verfahren zur herstellung von hochkonzentrierten, niedrigviskosen, waessrigen loesungen von melamin/aldehydharzen
GB9300704D0 (en) 1993-01-15 1993-03-03 Sandoz Ag Organic compounds
DE4411797A1 (de) 1994-04-06 1995-10-12 Sueddeutsche Kalkstickstoff Verfahren zur Herstellung von Sulfanilsäure enthaltenden Kondensationsprodukten auf Basis von Amino-s-triazinen
DE19609614A1 (de) 1995-03-17 1996-09-19 Sueddeutsche Kalkstickstoff Wasserlösliche Polykondensationsprodukte auf Basis von Amino-s-triazinen und deren Verwendung
DE19538821A1 (de) 1995-03-31 1996-10-02 Sueddeutsche Kalkstickstoff Kondensationsprodukte auf Basis von Amino-s-triazinen und deren Verwendung
MY114306A (en) 1995-07-13 2002-09-30 Mbt Holding Ag Cement dispersant method for production thereof and cement composition using dispersant
DE19834173A1 (de) 1997-08-01 1999-02-04 Sueddeutsche Kalkstickstoff Copolymere auf Basis von ungesättigten Dicarbonsäure-Derivaten und Oxyalkylenglykol-Alkenylethern
MXPA02012393A (es) * 2000-06-13 2005-04-19 Mineral Resource Technologies Composicion de cemento para albanileria y un metodo para hacerla.
DE102005008671A1 (de) 2005-02-25 2006-08-31 Construction Research & Technology Gmbh Phosphor-haltige Copolymere, Verfahren zu ihrer Herstellung und deren Verwendung
FR2904307B1 (fr) 2006-07-28 2008-09-05 Joseph Davidovits Ciment geopolymerique a base de cendres volantes et a grande innocuite d'emploi.
DE102008010795A1 (de) 2008-02-23 2009-08-27 Basf Construction Polymers Gmbh Additiv zum Zementieren von Bohrlöchern
US8277556B2 (en) * 2009-06-05 2012-10-02 W. R. Grace & Co.-Conn. Articles made from cementitious foam and slurry
EP2463314A1 (fr) 2010-12-10 2012-06-13 Sika Technology AG Fabrication de polymères en peigne par transestérification
EP2687498A1 (fr) 2012-07-20 2014-01-22 Construction Research & Technology GmbH Additif pour masses se détachant hydrauliquement
CA2997520A1 (fr) * 2015-09-07 2017-03-16 De Cavis Ag Poudre de formation de mousse catalytiquement active
CA3055003A1 (fr) 2017-03-06 2018-09-13 Construction Research & Technology Gmbh Mousse inorganique a base de sulfoaluminate de calcium
MY196377A (en) * 2017-10-20 2023-03-27 Construction Research & Technology Gmbh Set Control Composition for Cementitious Systems
ES2991355T3 (es) * 2021-05-10 2024-12-03 Wacker Chemie Ag Uso de mortero celular como adhesivo para revestimientos de suelos

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CN120693311A (zh) 2025-09-23

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