EP3938212A1 - Composition de liants minéraux pour l'impression 3d - Google Patents

Composition de liants minéraux pour l'impression 3d

Info

Publication number
EP3938212A1
EP3938212A1 EP20709604.1A EP20709604A EP3938212A1 EP 3938212 A1 EP3938212 A1 EP 3938212A1 EP 20709604 A EP20709604 A EP 20709604A EP 3938212 A1 EP3938212 A1 EP 3938212A1
Authority
EP
European Patent Office
Prior art keywords
binder composition
weight
water
dry
mineral
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
EP20709604.1A
Other languages
German (de)
English (en)
Inventor
Gary Boon
Maxime LIARD
Didier Lootens
Lolita HAUGUEL
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 EP3938212A1 publication Critical patent/EP3938212A1/fr
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • 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
    • C04B28/06—Aluminous cements
    • C04B28/065—Calcium aluminosulfate cements, e.g. cements hydrating into ettringite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B1/00—Producing shaped prefabricated articles from the material
    • B28B1/001—Rapid manufacturing of 3D objects by additive depositing, agglomerating or laminating of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28C—PREPARING CLAY; PRODUCING MIXTURES CONTAINING CLAY OR CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28C5/00—Apparatus or methods for producing mixtures of cement with other substances, e.g. slurries, mortars, porous or fibrous compositions
    • B28C5/02—Apparatus or methods for producing mixtures of cement with other substances, e.g. slurries, mortars, porous or fibrous compositions without using driven mechanical means effecting the mixing
    • B28C5/06—Apparatus or methods for producing mixtures of cement with other substances, e.g. slurries, mortars, porous or fibrous compositions without using driven mechanical means effecting the mixing the mixing being effected by the action of a fluid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28C—PREPARING CLAY; PRODUCING MIXTURES CONTAINING CLAY OR CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28C5/00—Apparatus or methods for producing mixtures of cement with other substances, e.g. slurries, mortars, porous or fibrous compositions
    • B28C5/08—Apparatus or methods for producing mixtures of cement with other substances, e.g. slurries, mortars, porous or fibrous compositions using driven mechanical means affecting the mixing
    • B28C5/0875—Mixing in separate stages involving different containers for each stage
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28C—PREPARING CLAY; PRODUCING MIXTURES CONTAINING CLAY OR CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28C5/00—Apparatus or methods for producing mixtures of cement with other substances, e.g. slurries, mortars, porous or fibrous compositions
    • B28C5/08—Apparatus or methods for producing mixtures of cement with other substances, e.g. slurries, mortars, porous or fibrous compositions using driven mechanical means affecting the mixing
    • B28C5/10—Mixing in containers not actuated to effect the mixing
    • B28C5/12—Mixing in containers not actuated to effect the mixing with stirrers sweeping through the materials, e.g. with incorporated feeding or discharging means or with oscillating stirrers
    • B28C5/1238—Mixing in containers not actuated to effect the mixing with stirrers sweeping through the materials, e.g. with incorporated feeding or discharging means or with oscillating stirrers for materials flowing continuously through the mixing device and with incorporated feeding or discharging devices
    • B28C5/1253—Mixing in containers not actuated to effect the mixing with stirrers sweeping through the materials, e.g. with incorporated feeding or discharging means or with oscillating stirrers for materials flowing continuously through the mixing device and with incorporated feeding or discharging devices with discharging devices
    • B28C5/1261—Applying pressure for discharging
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing
    • 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
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/26—Carbonates
    • C04B14/28—Carbonates of calcium
    • 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
    • C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
    • C04B22/08—Acids or salts thereof
    • C04B22/14—Acids or salts thereof containing sulfur in the anion, e.g. sulfides
    • C04B22/142—Sulfates
    • C04B22/148—Aluminium-sulfate
    • 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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2641—Polyacrylates; Polymethacrylates
    • C04B24/2647—Polyacrylates; Polymethacrylates containing polyether side chains
    • 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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/38—Polysaccharides or derivatives thereof
    • C04B24/383—Cellulose or derivatives thereof
    • 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
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients
    • C04B40/0042—Powdery mixtures
    • 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
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/06—Inhibiting the setting, e.g. mortars of the deferred action type containing water in breakable containers ; Inhibiting the action of active ingredients
    • C04B40/0608—Dry ready-made mixtures, e.g. mortars at which only water or a water solution has to be added before use
    • 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
    • C04B2103/0068—Ingredients with a function or property not provided for elsewhere in C04B2103/00
    • C04B2103/0079—Rheology influencing 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
    • C04B2103/10—Accelerators; 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
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
    • C04B2103/32—Superplasticisers
    • 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
    • C04B2103/50—Defoamers, air detrainers
    • 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
    • C04B2111/00034—Physico-chemical characteristics of the mixtures
    • C04B2111/00181—Mixtures specially adapted for three-dimensional printing (3DP), stereo-lithography or prototyping

Definitions

  • the invention relates to a mineral binder composition, its use for the 3D printing of moldings and a method for
  • Structural concrete is usually poured into formwork for shaping and allowed to harden in it.
  • the manufacture of the formwork causes
  • 3D printing also called “generative manufacturing process”, “generative manufacturing” or “freeform construction”, refers to processes in which a spatial object or a spatial object is created through targeted spatial deposition, application and / or solidification of material Molded body is produced.
  • the material is deposited, applied and / or solidified, in particular using a data model of the object to be produced, and in particular in layers or layers.
  • the material is typically applied using a 3D printer. Every object is generative
  • a shapeless material is used to manufacture an object, which is particularly subjected to chemical and / or physical processes (e.g. melting, polymerizing, sintering, curing).
  • cementitious binder compositions especially mortar or concrete
  • a water-based cementitious binder is used for this
  • composition prepared and conveyed to a movable print head of a 3D printer.
  • the computer controlled, in at least one
  • the printhead deposits the material in a specified quantity and speed, typically in layers, until the desired one
  • the top layer in each case is advantageously not yet fully cured when the next layer above is applied, so that a good bond between the individual layers is ensured.
  • cement achieves its strength through reaction with water in a chemical process known as cement hydration. This reaction is also known as the setting of the cement. Typically, the time between mixing the cement with water and achieving sufficient strength to be dimensionally stable and stable is in the range of several hours.
  • EP 3 421 201 describes a cementitious mixture for 3D printing.
  • Mixture comprises a hydraulic binder, latent hydraulic additives, fillers, aggregates, further additives and water.
  • the aggregates must have a particle size of less than 1 mm and the viscosity of the mixture is between 4 ⁇ 00 and 35 ⁇ 00 Pa s.
  • the mortar mixing time is very long, and the printing speed and printing height are low.
  • WO 2019030255 describes a method for 3D printing in which a water-containing mineral binder composition is conveyed to a continuous mixer with a pump and mixed with an aqueous setting accelerator in the continuous mixer. The now accelerated binder composition is applied in layers by means of a print head. Mixing the accelerator into the binder
  • composition with a continuous mixer which is preferred on
  • the printhead is mounted is an additional step and greatly increases the cost of installing the printer.
  • the object of the present invention is to provide an improved mineral
  • the composition should in particular be an efficient, simple, inexpensive, enable reliable and rapid application. This, if possible, with a high quality of the applied layers in terms of strength development and optical uniformity.
  • the dry mineral binder composition is easy to use
  • the dry mineral binder composition already contains
  • Accelerator the addition of accelerator at or just before the print head, is not necessary.
  • the dry mineral binder composition can be processed quickly with water to form a homogeneous water-containing binder composition. This enables continuous mixing, which is advantageous for homogeneous processability and high print quality.
  • the stability of the applied layers is high and they quickly achieve sufficient strength to support additional layers applied over them without deforming. This enables rapid printing, also in the vertical direction.
  • Aluminum sulfate based accelerators are typically used for
  • Shotcrete used.
  • an aqueous accelerator solution or suspension is added to a non-accelerated concrete mix directly at the spray nozzle.
  • the accelerated concrete is sprayed on a wall and immediately stiffens.
  • an accelerator based on aluminum sulphate can be used in the binder composition according to the invention without leading to an immediate stiffening of the mixture after mixing with water.
  • the water-based binder composition remains easy to process over a sufficient period of time so that it can be easily processed using 3D Printer can be applied and can also form a good bond with a later applied new layer.
  • Conditions such as, for example, the ambient temperature, the desired vertical printing speed and the desired printing height can be adjusted only by varying the amount of polycarboxylate ether.
  • Polycarboxylate ether in the binder composition can be different in order to ensure optimal strength development for both applications. This is very advantageous because, by varying a single component, a binder composition adapted to the respective setting parameters can be made available.
  • Binder composition high printing speed, printing heights over a meter and more, as well as homogeneous and aesthetic moldings without cracks can be obtained.
  • the invention relates to a dry mineral binder composition comprising cement and mineral fillers for the production of molded bodies by means of 3D printing, characterized in that the
  • Binder composition also comprises at least one accelerator based on aluminum sulfate, at least one superplasticizer based on a polycarboxylate ether and at least one rheological aid, the polycarboxylate ether, assuming all carboxylic acid groups are present as free acid, at least 1 mmol, in particular at least 1.2 mmol, in particular at least 1.8 mmol, Carboxylic acid groups per gram dry
  • 3D printing also known as “freeform construction” is understood to be a form-free, shaping process.
  • a deformable material is applied in several layers or in smaller portions, one on top of the other and, if necessary, next to one another, layer by layer, thus creating three-dimensional objects.
  • the construction is computer-controlled according to given dimensions and shapes. After the material which is deformable during application has hardened, a solid shaped body is formed.
  • the layers are typically not applied by spraying the material.
  • mineral binder is understood in particular to mean a binder which, in the presence of water, reacts in a hydration reaction to form solid hydrates or hydrate phases.
  • mineral binder composition is accordingly understood to mean a composition containing at least one mineral binder. This contains in particular the binder, fillers and optionally one or more additives.
  • dry mineral binder composition means a free-flowing mineral binder composition with a moisture content of less than 0.5% by weight.
  • water-containing mineral binder composition means a mineral binder composition mixed with water, in particular in fluid form.
  • polycarboxylate ether is understood to mean a
  • Comb polymer comprising a backbone of hydrocarbons with attached carboxylic acid groups or their salts and also to the
  • the side chains are attached to the polycarboxylate backbone in particular via ester, ether, imide and / or amide groups.
  • the amount of carboxylic acid groups in the polycarboxylate ether is expressed in millimoles of carboxylic acid groups in one gram of the
  • Polycarboxylate ethers (mmol / g) understood.
  • any salts of the carboxylic acids that may be present are counted among the carboxylic acid groups and the weight of the polycarboxylate ether is used in non-neutralized form.
  • the amount of carboxylic acid groups in the polycarboxylate ether can be any amount of carboxylic acid groups in the polycarboxylate ether.
  • the amount of carboxylic acid groups in the polycarboxylate ether can be any amount of carboxylic acid groups in the polycarboxylate ether.
  • Mn (BB) average molecular weight of the polycarboxylate backbone in g / mol
  • M (monomer) average molecular weight of the monomers of
  • m (BB) weight of the polycarboxylate backbone in g during the production of the polycarboxylate ether
  • n a (SK) amount of substance of the a.
  • Polycarboxylate ethers corresponds to the quotient from the initial weight of the a.
  • Mn (polymer) mean molar mass of the polycarboxylate ether in g / mol.
  • the mean molar mass of the polycarboxylate ether used is determined in particular using GPC against PEG as the standard.
  • a polycarboxylate ether is produced by transesterification of a
  • the initial weight of the polyacrylic acid is 100 g, the weight of the methoxy-terminated one
  • Polyethylene glycol is 150 g. This information results in:
  • ns amount of moles of the carboxylic acid groups contained in the monomers used to produce the polycarboxylate ether
  • m (Monomera) weight of the a.
  • rheological aid is understood to mean a substance which can change the theological properties of the water-containing mineral binder composition, in particular it increases the viscosity, the flow limit and / or the thixotropy.
  • dimensional stability is understood to mean a material property in which the material changes the individual dimensions by a maximum of 10% after shaping, provided that no external force other than
  • “stability” is understood to mean the strength that a hardenable material has after application before hardening.
  • cements classified under DIN EN 197-1 Portland cement (CEM I), Portland composite cement (CEM II), Floch-furnace slag cement (CEM III), Pozzolan cement ( CEM IV) and composite cement (CEM V).
  • CEM I Portland cement
  • CEM II Portland composite cement
  • CEM III Floch-furnace slag cement
  • CEM IV Pozzolan cement
  • CEM V composite cement
  • cements that are produced according to an alternative standard such as the ASTM standard are equally suitable.
  • Portland cement CEM I or CEM II according to DIN EN 197-1 is preferred.
  • Portland cement CEM I 42.5 or CEM I 52.5 is particularly preferred. Such cements give good strength and good workability.
  • the dry mineral binder composition advantageously also contains at least one latently hydraulic or pozzolanic binder,
  • the latently hydraulic or pozzolanic binder is preferably present in 0.1 to 10% by weight, in particular in 0.5 to 5% by weight, based on the total weight of the dry binder composition.
  • the dry mineral binder composition contains mineral fillers.
  • Fillers are chemically inert solid particulate materials and are available in different shapes, sizes and as different materials, which vary from the finest sand particles to large coarse stones. In principle, all fillers that are commonly used for concrete and mortar are suitable. Examples of particularly suitable fillers are aggregates, gravel, sand, in particular quartz sand, limestone sand and slag sand, crushed stones, calcined pebbles or light fillers such as expanded clay, expanded glass, foam glass, pumice stone, perlite and vermiculite. Further advantageous fillers are fine or very fine fillers such as ground limestone or dolomite,
  • Preferred fillers are selected from the group consisting of quartz sand, quartz powder, limestone sand, ground limestone and ground steel slag.
  • the filler preferably comprises at least one finely ground crystalline filler, in particular limestone. This can promote the early strength development of the binder composition mixed with water.
  • the particle size of the fillers depends on the application and is in the range from 0.1 ⁇ m to 32 mm and more. Different particle sizes are preferably mixed in order to optimally adjust the properties of the binder composition. Fillers made from different materials can also be mixed. The particle size can be determined with the help of a sieve analysis.
  • Fillers with particle sizes of at most 8 mm, more preferably at most 5 mm, even more preferably at most 3.5 mm, most preferably at most 2.2 mm, in particular at most 1.2 mm or at most 1.0 mm are preferred.
  • the particle size is determined in particular by the planned layer thickness of the applied layers in 3D printing.
  • a maximum particle size of the fillers is sensibly as large as the planned one
  • the binder composition preferably contains 20 to 40% by weight, in particular 22 to 36% by weight, based on the total weight of the dry binder composition, fine fillers with a particle size of less than 0.125 mm.
  • Suitable fillers with a small particle size are particularly fine
  • the binder composition preferably contains 1 to 10% by weight, more preferably 2 to 5% by weight, of ground calcium carbonate with a
  • the very fine calcium carbonate improves the workability of the binder composition mixed with water and can increase the strength development of the binder composition.
  • fillers with particle sizes up to 32 mm, more preferably up to 20 mm, most preferably up to 16 mm, can also be used.
  • Particle sizes can be determined using sieve analysis in accordance with the ASTM C136 and ASTM C117 standards.
  • the mineral fillers are preferably 45 to 85% by weight, in particular 50 to 80% by weight, based on the total weight of the dry ones
  • Binder composition present.
  • the dry mineral binder composition contains one
  • Aluminum sulfate based accelerator Aluminum sulfate based accelerator.
  • the accelerator causes the strength to develop rapidly
  • Binder composition after mixing with water.
  • the accelerator advantageously contains at least 30% by weight, preferably at least 35% by weight, more preferably at least 40% by weight,
  • Aluminum sulphate calculated as aluminum sulphate Flydrat Al2 (S04) 3-16 FI2O.
  • the accelerator can advantageously contain other components such as amino alcohols, alkali and alkaline earth nitrates, alkali and
  • a particularly preferred binder composition consists of
  • accelerator is composed of aluminum sulfate hydrate or is aluminum sulfate hydrate.
  • the binder composition is preferably free from amino alcohols.
  • Amino alcohols have an intense, unpleasant odor, can be hazardous to health and lead to uncontrolled stiffening of the binder composition after mixing with water.
  • the aluminum sulfate-based accelerator is preferably present in 0.1 to 2% by weight, more preferably in 0.3 to 1.5% by weight, in particular in 0.4 to 1.0% by weight, based on the total weight of the dry binder composition.
  • Such a dosage of the accelerator, in particular in combination with a polycarboxylate ether, leads to a rapid development of the strength of the binder composition mixed with water without impairing the processability for the printing process.
  • the dry mineral binder composition comprises at least one superplasticizer based on polycarboxylate ether.
  • the at least one polycarboxylate ether contains carboxylic acid groups in the form of free, that is, non-neutralized, carboxylic acid groups and / or in the form of their alkali metal and / or alkaline earth metal salts.
  • a polycarboxylate ether which has no other anionic groups in addition to the carboxylic acid groups is preferred.
  • a polycarboxylate ether whose side chains consist of at least 80 mol%, preferably at least 90 mol%, especially preferably 100 mol%, of ethylene glycol units is further preferred.
  • the side chains preferably have an average molecular weight M w in the range from 500 to 10 ⁇ 00 g / mol, preferably 800 to 8 ⁇ 00 g / mol, particularly preferably 1 ⁇ 00 up to 500 g / mol.
  • M w average molecular weight in the range from 500 to 10 ⁇ 00 g / mol, preferably 800 to 8 ⁇ 00 g / mol, particularly preferably 1 ⁇ 00 up to 500 g / mol.
  • Preferred is a polycarboxylate ether of methacrylic acid and / or
  • Acrylic acid units and monomer units with polyalkylene glycol chains is built up.
  • the at least one polycarboxylate ether preferably has a medium one
  • Such polycarboxylate ethers have a good effect, even in the presence of the accelerator based on aluminum sulfate and with a low water content
  • a low water content causes a high strength of a cured material
  • such polycarboxylate ethers act particularly well as a means of controlling the setting and / or setting of the water-containing binder composition.
  • the at least one polycarboxylate ether can be added as an aqueous solution to the
  • Binder composition are introduced, for example by
  • the at least one polycarboxylate ether is preferably present as a powder in the dry binder composition.
  • the at least one polycarboxylate ether has a block or gradient structure.
  • polycarboxylate ether with a block or gradient structure is understood to mean a polymer in which the monomer units are present in a non-statistical sequence, that is, the sequence is not obtained by chance. Included in the polycarboxylate ether of block or gradient structure
  • Such block or gradient polymers therefore have sections with a high density of anionic groups and sections which contain no or only a few anionic groups.
  • Binder composition and water is very short, especially for continuous mixing.
  • Polycarboxylate ethers with a block or gradient structure also cause the water-containing binder composition to have a low viscosity. This improves the pumpability of the binder composition mixed with water.
  • the good liquefying effect of the polycarboxylate ethers with a block or gradient structure also surprisingly persists in the inventive one
  • Binder composition only for a few minutes, which is advantageous for 3D printing because it makes the
  • Binder composition can be achieved directly after mixing with water and good stability of the water-containing binder composition after application.
  • the at least one polycarboxylate ether is preferably present in 0.02 to 5% by weight, more preferably in 0.05 to 4% by weight, in particular in 0.1 to 3% by weight, calculated as dry polymer based on the total weight of the dry binder composition.
  • the metering of the at least one polycarboxylate ether in the binder composition is advantageously adapted to the respective printing task.
  • the printing parameters such as typically the desired height of the molding, the thickness of the applied layers, the printing speed and the expected ambient temperature, are advantageously recorded before printing and then using empirical values, tables and / or computer program determines the optimal amount of polycarboxylate ether in the binder composition.
  • Polycarboxylate ether in the binder composition can be different in order to ensure optimal strength development for both applications.
  • Binder composition provided.
  • Molded body has different parts with different dimensions if only part of the polycarboxylate ether in the dry
  • Binder composition is present and another part, in each case adapted to the current printing conditions, is added during or shortly after mixing with water.
  • the further part of the polycarboxylate ether is advantageously added together with the mixing water in a continuous mixing process.
  • the dry binder composition can thus be produced in large quantities, which is advantageous, and the adjustment of the properties of the
  • the dry mineral binder composition contains at least one organic and / or inorganic rheological aid.
  • Suitable rheology aids are in particular modified starch
  • Amylopectin modified cellulose, microbial polysaccharides, galactomannans, Alginate, tragacanth, polydextrose, superabsorbent or mineral
  • the rheological aid is preferably selected from the group consisting of modified starches, modified celluloses, microbial polysaccharides, superabsorbents and mineral thickeners.
  • the total amount of rheological aid in the dry binder composition is preferably from 0.01 to 5% by weight, based on the
  • the modified starch is preferably a starch ether, in particular
  • the modified starch is preferably present in 0.01 to 2% by weight based on the total weight of the dry binder composition.
  • the modified cellulose is preferably methyl cellulose, ethyl cellulose,
  • the microbial polysaccharide is preferably welan gum, xanthan gum or diutan gum and is preferably present in 0.01 to 0.1% by weight, based on the total weight of the dry binder composition.
  • the superabsorbent is preferably selected from the group comprising
  • Polyacrylamide polyacrylonitrile, polyvinyl alcohol, isobutylene-maleic anhydride copolymers, polyvinylpyrrolidone, homo- and copolymers of monoethylenically unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, sorbic acid, maleic acid, fumaric acid, itaconic acid, preferably polyacrylic acid, which can be partially or completely neutralized Copolymers and terpolymers of the monoethylenically unsaturated carboxylic acids mentioned with vinylsulfonic acid, (meth) acrylamidoalkylsulfonic acids, allylsulfonic acid, vinyltoluenesulfonic acid, Vinylphosphonic acid, (meth) acrylamide, N-alkylated (meth) acrylamide, N-methylol (meth) acrylamide, N-vinylformamide, N-vinyl acetamide, vinyl pyrrolidone,
  • the superabsorbent homo- and copolymers can be linear or branched, the copolymers can be present randomly or as block or gradient polymers.
  • the homopolymers and copolymers are preferably also crosslinked.
  • the superabsorbent is preferably polyacrylic acid, which can be partially or completely neutralized and is crosslinked.
  • the superabsorbent is preferably present in 0.01 to 0.5% by weight, in particular in 0.05 to 0.3% by weight, based on the total weight of the dry binder composition.
  • the mineral thickener is preferably a special silicate or clay mineral, in particular a bentonite or sepiolite, preferably sepiolite.
  • the mineral thickener is preferably present in 0.1 to 1% by weight based on the total weight of the dry binder composition.
  • the binder composition preferably contains at least two, more preferably at least three, different rheological aids.
  • the rheological aid is particularly suitable, the dimensional stability of the
  • Preferred combinations of two or more rheology aids are:
  • the different thickening properties of the rheological aids can be optimally matched to one another. This results in good processability with good stability of the water-containing binder composition.
  • a combination of rheological aids which comprises at least one superabsorbent is particularly preferred.
  • the superabsorbent also acts as a means of reducing shrinkage, which is particularly advantageous.
  • the dry mineral binder composition preferably also contains 0.1 to 5% by weight, preferably 0.1 to 4.5% by weight, more preferably 0.5 to 3% by weight, calcium sulfoaluminate, based on the total weight of the dry binder composition.
  • a suitable calcium sulfoaluminate is available, for example, in Denka CSA # 20, available from Newchem, Switzerland.
  • the calcium sulfoaluminate can, especially in the preferred dosage, on the one hand increase the early strength development of the aqueous binder composition and at the same time reduce shrinkage.
  • a higher content of calcium sulfoaluminate in the binder composition can reduce the ultimate strength of a printed molded article and increase the cost of the composition.
  • the combination of calcium sulfoaluminate and rheological aid, in particular a superabsorbent can reduce the shrinkage of the Binder composition can be greatly reduced after application.
  • Shrinkage can lead to the formation of cracks in the molded article produced. Cracks can reduce the durability of the printed structures and disrupt the visual impression.
  • the dry mineral binder composition advantageously also contains at least one further additive for reducing shrinkage selected from the group consisting of glycols, polyglycols and water-storing materials, such as, in particular, porous stones, ground bricks and / or ground cement stone.
  • the dry mineral binder composition preferably also contains at least one defoamer, in particular selected from the group consisting of oil-based defoamers, in particular defoamers based on mineral oils, vegetable oils or white oils which can contain a wax and / or hydrophobic silica, silicone-based defoamers which, for example, Alkoxylation or fluorination can be modified, alkyl esters of phosphoric or phosphonic acid, alkoxylated polyols, especially ethoxylated diols, fatty acid-based defoamers, especially mono- and diglycerides of fatty acids and alkoxylated fatty alcohols, and mixtures thereof.
  • defoamer in particular selected from the group consisting of oil-based defoamers, in particular defoamers based on mineral oils, vegetable oils or white oils which can contain a wax and / or hydrophobic silica, silicone-based defoamers which, for example, Alkoxylation or fluor
  • the defoamer is preferably selected from the group comprising
  • Fatty alcohol alkoxylates and polysiloxane and a combination of mineral oil and a silicone oil containing hydrophobic silica Fatty alcohol alkoxylates and polysiloxane and a combination of mineral oil and a silicone oil containing hydrophobic silica.
  • the defoamer is preferably present in 0.01 to 1% by weight, in particular 0.1 to 0.8% by weight, based on the total weight of the dry binder composition.
  • a defoamer is advantageous because it prevents or reduces the formation of air voids when the dry binder composition is mixed with water. Air voids can promote the water-containing binder composition interfere with the print head, and reduce the strength in the cured molded body and pores interfere with the visual impression of the molded body.
  • the defoamer also reduces the shrinkage and thus the formation of cracks in the cured molding.
  • the dry mineral binder composition can also contain at least one further additive, for example a concrete additive and / or a mortar additive.
  • the at least one further additive includes in particular a flow agent, a retarder, a wetting agent, fibers, a dye, a preservative, a further accelerator
  • Dispersion polymer a cationic polymer, a cationic polycondensate, a cationic comb polymer, an air entrainer, another
  • Shrinkage reducer or a corrosion inhibitor, or combinations thereof are examples of Shrinkage reducer or a corrosion inhibitor, or combinations thereof.
  • the flow agent is in particular sodium gluconate, lignosulfonate, sulfonated naphthalene-formaldehyde condensate, sulfonated melamine-formaldehyde condensate, sulfonated vinyl copolymer, polyalkylene glycol
  • Phosphonate groups polyalkylene glycol with phosphate groups or a
  • aromatic condensate with phosphonate groups and polyalkylene glycol chains aromatic condensate with phosphonate groups and polyalkylene glycol chains.
  • the use of hardening retarders can be advantageous, since this extends the processing time of the water-based binder composition.
  • the hardening retarder is preferably a hydroxycarboxylic acid, in particular tartaric acid, citric acid or gluconic acid, a sugar, in particular sucrose, a phosphate or a phosphonate, or their salts or mixtures thereof.
  • a preferred binder composition comprises:
  • cement especially Portland cement, - 0.1 to 5% by weight, preferably 0.1 to 4.5% by weight, more preferably 0.5 to 3% by weight, calcium sulfoaluminate,
  • At least one latent hydraulic binder in particular metakaolin and / or silica dust,
  • Another object of the invention is a water-containing mineral binder composition, obtained by mixing the dry mineral binder composition, as described above, with water, in particular with 10 to 25% by weight, preferably 12 to 22% by weight, more preferably 14 to 20% by weight %, Water based on that
  • Mixing with water is preferably carried out in a continuous mixer. This ensures a high production speed. In addition, in the event of a possible interruption, there does not have to be a discontinuous
  • the start of setting of the water-containing binder composition is advantageously between about 10 minutes and 1 hour, and the end of setting between about 30 minutes and 3 hours, measured in accordance with DIN EN 196-3 at 20 ° C with an automatic Vicat apparatus.
  • the water-containing binder composition advantageously achieves a strength of at least 0.05 MPa, preferably at least 0.08 MPa, in particular at least 0.1 MPa, at 20 ° C. one hour after application, and after 3 hours, preferably 2 hours, at least 0.5 MPa, in particular 1 MPa.
  • the strength can be determined using a penetration method such as described in ASTM C 403.
  • Such a strength development of the water-containing binder composition is particularly advantageous for the efficient production of moldings.
  • the invention also relates to the use of the water-containing mineral binder composition for the production of moldings by means of 3D printing.
  • Another object of the invention is a method for applying a mineral binder composition, in particular by means of 3D printing, comprising the steps:
  • Binder composition
  • Binder composition with the movable printhead is advantageous
  • Binder composition added together with the water, the at least one further additive being another
  • Polycarboxylate ether Polycarboxylate ether, a retarder and / or another
  • Rheology aid in particular a polycarboxylate ether, comprises, and
  • print height Depending on printing conditions such as horizontal and vertical printing speed, print height and ambient temperature.
  • the at least one further additive is preferably a polycarboxylate ether, a retarder and / or a rheological aid, as described above.
  • the further polycarboxylate ether is preferably identical to the polycarboxylate ether in the dry mineral binder composition, but is here in particular as an aqueous solution.
  • the further polycarboxylate ether is not identical to the polycarboxylate ether in the dry mineral binder composition.
  • the other differs
  • Polycarboxylate ether of the polycarboxylate ether in the dry mineral binder composition by the number of carboxylic acid groups per g of polymer and / or the average molecular weight Mw of the polyalkylene glycol side chains or it has a block or gradient structure if the polycarboxylate ether in the dry binder composition does not have a block or gradient structure .
  • the further polycarboxylate ether if present, is preferably added in 0.01 to 5% by weight, in particular in 0.08 to 4% by weight, based on the weight of the water-containing binder composition.
  • the retarder if present, is preferred in 0.01 to 3% by weight, in particular in 0.03 to 2% by weight, based on the weight of the
  • hydrous binder composition added.
  • the further rheology aid if present, is preferably added in 0.01 to 2% by weight, based on the weight of the water-containing binder composition
  • the strength development of the binder composition can be continuously adapted to the printing process, resulting in a high quality structure of the molded body despite the possible
  • Printing speed and / or interruptions in the printing process allows.
  • At least one property of the applied material is determined during the printing process and, if the property deviates from the specified setpoint values, the further additive, in particular a polycarboxylate ether, is added
  • Retarder and / or a rheological aid metered into the mixing device.
  • At least one further rheology aid in particular a modified cellulose and / or a microbial polysaccharide, preferably in the form of an aqueous solution, can be introduced into the water-containing binder composition, in particular by means of a pump attached to or just in front of the print head . This can cause unwanted fluctuations in the stability of the
  • water-containing binder composition are balanced.
  • molded bodies can be produced homogeneously and quickly by applying them in layers.
  • the printing speed that is, the speed of the horizontal
  • Movement of the print head preferably at least 20 mm per second, more preferably at least 30 mm per second, in particular at least 40 mm per second.
  • the vertical printing speed depends on the horizontal dimension of the molding, the thickness of the individual applied layers and the horizontal printing speed.
  • the period of time between the application of the lower layer and the next layer above is preferably between about 1 second and 30 minutes, in particular between 10 seconds and 10 minutes.
  • Another object of the present invention is a molded body produced by mixing a dry mineral
  • Binder composition as described above, with water and optionally further additives, application of the water-containing mineral binder composition in layers with a 3D printer and hardening of the binder composition.
  • the height of an individual layer is preferably 0.2 mm to 200 mm, more preferably 1 mm to 100 mm, in particular 2 mm to 50 mm .
  • the total height of the shaped body or the thickness of all individual layers of the shaped body taken together is preferably 0.01 m to 100 m or more, more preferably 0.1 m to 80 m, even more preferably 0.3 m to 30 m, in particular 0.5 m to 10 m.
  • the shaped body preferably has a height of at least 0.5 m, more preferably at least 1 m, in particular at least 1.5 m or 2 m.
  • the surface of the shaped body can be smoothed, repaired or specially deformed with suitable tools. This can be done as part of the machine production, or manually as a separate step.
  • the surface can also be given a functional or decorative
  • Coating are provided, for example with a color.
  • the shaped body can also, as long as it is still workable, with suitable
  • the shaped body produced by the method according to the invention can have almost any shape.
  • the molded body is, for example, a building, a prefabricated part for a building, a component, a brickwork, a bridge, a column, a decorative element such as artificial mountains, reefs or sculptures, a basin, a fountain or a tub.
  • Shaped bodies represent a full shape or a hollow shape, with or without a bottom.
  • the shaped body can be created directly on site and no longer moved after application.
  • the shaped body can also be created at another location, in particular special in a factory. This is preferably done on a pad to which he is not liable. After curing, the molded body can be transported to the desired location.
  • Fig. 1 shows: a schematic representation of an exemplary system for
  • Binder composition
  • FIG. 2 shows a graphical representation of the development of strength over time of water-containing cementitious binder compositions.
  • FIG. 1 an exemplary system 1 for carrying out a method according to the present invention for applying the water-containing mineral binder composition is shown schematically.
  • the system 1 comprises a movement device 2 with a movable arm 2.1. At the free end of the arm 2.1 a print head 3 is attached, which can be moved in all three spatial dimensions by the arm 2.1. The print head 3 can thus be moved to any position in the working area of the
  • Moving device 2 are moved.
  • the print head 3 has in the interior one from the end face facing the arm 2.1 (top in FIG. 1) to the opposite and free end face
  • An inlet nozzle 5 for adding an additive opens laterally into the passage 3.1 in an area facing the arm 2.1.
  • an additive for example a
  • a static mixer 6 is furthermore arranged in the passage 3.1, which additionally mixes the water-containing mineral binder composition and the additive as it flows through.
  • a measuring unit 8 for determining the pressure in the tubular passage 3.1 is also arranged.
  • the sampling rate of the measuring unit 8 is e.g. 10 Hz.
  • a device 7 for venting the water-containing mineral binder composition is also attached to the print head 3.
  • the device is designed as a vacuum treatment device and makes it possible to reduce the proportion of air in the water-containing mineral binder composition.
  • a section of the wall of the passage 3.1 can be designed as a gas-permeable membrane, so that by applying a negative pressure outside the passage 3.1, air is drawn from the water-containing mineral binder composition.
  • the binder composition also has a feed device 9, which on the inlet side corresponds to three containers 11.1, 11.2, 11.3 and a reservoir 11.4. In each of the three containers 11.1, 11.2, 11.3 there is a component of the water-containing mineral binding agent
  • the first component which is present in the first container 11.1, is a dry mineral binder composition.
  • the second component which is present in the second container 11.2, consists for example of water.
  • the third component present in the third container 11.3 is e.g. a flow agent in the form of a polycarboxylate ether.
  • the feed device 9 On the outlet side, the feed device 9 has three separate outlets, each with one of three inlets 10.1, 10.2, 10.3 of a mixing device 10 are connected.
  • the feed device 9 also has individually controllable metering devices (not shown in FIG. 1) so that the individual
  • Components in the individual containers 11.1, 11.2, 11.3 can be dosed individually into the mixing device 10.
  • Another outlet of the feed device is connected to the inlet nozzle 5 (not shown in FIG. 1), so that the
  • Feed device 9 additive can be conveyed from the reservoir 11.4 into the inlet nozzle 5.
  • the mixing device 10 is designed as a dynamic mixer and, in addition to this, comprises an integrated conveying device in the form of a screw conveyor.
  • the mixing device the individually metered components are mixed with one another and conveyed into the flexible line 12 attached to the mixing device on the outlet side.
  • the mixing and conveying of the binder composition can take place continuously.
  • the front side of the print head opens into the tubular passage 3.1, the water-containing mineral binder composition can be conveyed into the print head 3 and applied continuously through the controllable outlet 4.
  • the measuring unit 13 which is integrated in the conveying line 12 in the area between the mixing device 10 and the print head 3.
  • the measuring unit includes, for example, one
  • Ultrasonic transducer which is designed to determine the flow properties of the water-containing mineral binder composition.
  • a sampling rate of the measuring unit 13 is e.g. 10 Hz.
  • a central control unit 14 of the system 1 comprises a processor, a memory unit and several interfaces for receiving data and several interfaces for controlling individual components of the system 1.
  • the mixing device 10 is connected to the control unit 14 via a first control line 15a, while the feed device is connected to the control unit 14 via a second control line 15b.
  • the individual components in the containers 11.1, 11.2, 11.3 can be metered into the mixing device 10 via the central control unit according to prescribed recipes stored in the control unit and conveyed into the flexible line 12 at adjustable delivery rates.
  • Ventilation of the water-containing mineral binder composition on the print head are each also connected to the control unit 14 via a separate control line 15c, 15d, 15e and can be controlled or monitored by this.
  • the movement device 2 is also connected to the control unit 14 via a further control line 15g.
  • the movement of the print head 3 can thus be controlled via the control unit 14.
  • the measuring unit 8 is connected to the control unit 14 by a data line 15h, so that pressure data recorded in the measuring unit can be transmitted to the control unit 14.
  • the measuring unit 13 is connected to the control unit 14 with a data line 15f, so that data recorded in the measuring unit which contain the
  • the control unit 14 is programmed, for example, so that:
  • the conveying device integrated in the mixing device 10 is controlled as a function of the pressure 8 determined by the measuring unit 8 and the structure of the object to be produced with the water-containing mineral binder composition;
  • the dry mineral binder composition according to the invention has the composition described in Table 1.
  • Aluminum sulfate is Al2 (S04) 3 18 H2O, available from Merck, Switzerland.
  • Betoflow ® D is a fine calcium carbonate powder of around 1 -5 pm
  • Particle size available from Omya.
  • Nekafill ® 15 is a limestone powder, available from Kalkfabrik Netstal.
  • Sika ® ViscoCrete ® -225P is a powdery superplasticizer based on a polycarboxylate ether, available from Sika.
  • Carbowet ® 4000 is a defoamer, available from Air Products Chemicals Europe.
  • Denka CSA # 20 is a calcium sulfoaluminate cement based shrinkage reducer, available from Newchem, Switzerland.
  • the 3D printing was carried out with a system as shown by way of example in FIG. 1.
  • the dry binder composition with the composition shown in Table 1 was continuously with such an amount of water in the Mixer mixed to obtain a weight ratio of water to dry binder composition of about 0.16.
  • the water-containing mineral binder mixture was then mixed with the in the
  • Mixing device integrated screw conveyor conveyed via the flexible conveying line to the print head of the 3D printer.
  • Binder composition and the movement of the print head were controlled by a control unit.
  • the temperature of the mixing water and that of the ambient air was around 25 ° C.
  • the binder composition was applied with the printhead to a sheet of plastic laid out on a concrete floor in layers about 30 mm wide and 10 mm fleas.
  • the horizontal speed of the print head was about 40 mm per second.
  • a pipe with a diameter of about 0.6 m and a fleas of 2 meters was made in several vertical layers.
  • the molding was completed after about 2 hours and 40 minutes.
  • the fleas of the lower layers and the upper layers differed no more than 5%.
  • the printed molding had a wavy, very uniform surface with no visible defects. Even after 3 days of storage at 25 ° C. and about 40% relative humidity, the molded article showed no visible cracks.
  • the molding was destroyed with the aid of a heavy flame and the fragments were optically analyzed.
  • the fracture surfaces had a uniform surface, without air inclusions or defects.
  • Fracture surfaces showed no preferred orientation, that is, the
  • Example 1 was repeated while maintaining the printing parameters, but the binder composition did not contain any aluminum sulfate. Even before a pressure height of 0.3 m was reached, the structure collapsed.
  • a fresh mortar on 120 kg cement CEM I 52.5, 92 kg of quartz sand of 0-1 mm, 33 kg Betoflow ® -D 80 kg Nekafill ® 15, 0.6 kg Sika ® ® ViscoCrete -225P, 0004 kg Carbowet® 4000, 0.3 kg superabsorbent and 56.8 kg of water was prepared in a compulsory mixer.
  • Example 1 The application by means of a 3D printer was carried out as described in Example 1.
  • the mortar flowed out of the discharge nozzle and could not be applied in layers. The attempt was then canceled.
  • the static mixer 6 can be omitted, so that there is neither a static nor a dynamic mixer in the print head.
  • one or more further conveying devices can be provided in the conveying line 12 and / or in the print head 3. This can also involve other conveying devices than screw conveyors.
  • measuring unit which e.g. enable temperature measurement.
  • the mixing device 10 can also have fewer or more inlets, so that additional components that are present in additional containers can be metered in.
  • additional components that are present in additional containers can be metered in.
  • connections to external sources for example to a water connection, can also be provided.
  • control unit it is also possible to program the control unit differently, for example so that a volume flow through the delivery line 12 and / or the print head 3 is taken into account.

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Abstract

La présente invention concerne une composition sèche de liants minéraux comprenant du ciment et des charges minérales pour la fabrication de corps moulés au moyen d'une impression 3D. La composition de liants minéraux contient encore au moins un accélérateur à base de sulfate d'aluminium, au moins un super-fluidifiant à base d'un éther de polycarboxylate et au moins un adjuvant rhéologique.
EP20709604.1A 2019-03-15 2020-03-13 Composition de liants minéraux pour l'impression 3d Pending EP3938212A1 (fr)

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CN113354380B (zh) * 2021-06-28 2022-10-11 武汉理工大学 一种固废基热致促凝3d打印材料及其3d打印成型方法
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WO2024105002A1 (fr) * 2022-11-17 2024-05-23 Sika Technology Ag Matériaux cimentaires comprenant un composé luminescent pour l'impression de structures tridimensionnelles

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US20220162124A1 (en) 2022-05-26
BR112021013832A2 (pt) 2021-09-21
MX2021010729A (es) 2021-09-28
SG11202107329XA (en) 2021-08-30
CO2021013312A2 (es) 2021-12-10
CL2021001902A1 (es) 2022-04-01

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