US20170320128A1 - Method for constructing molds and cores layer by layer by means of a binder containing water glass, and a binder containing water glass - Google Patents

Method for constructing molds and cores layer by layer by means of a binder containing water glass, and a binder containing water glass Download PDF

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Publication number
US20170320128A1
US20170320128A1 US15/534,551 US201515534551A US2017320128A1 US 20170320128 A1 US20170320128 A1 US 20170320128A1 US 201515534551 A US201515534551 A US 201515534551A US 2017320128 A1 US2017320128 A1 US 2017320128A1
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Prior art keywords
binder
weight
less
layer
particularly preferably
Prior art date
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Abandoned
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US15/534,551
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English (en)
Inventor
Heinz Deters
Henning Zupan
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ASK Chemicals GmbH
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ASK Chemicals GmbH
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Assigned to ASK CHEMICALS GMBH reassignment ASK CHEMICALS GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DETERS, Heinz, ZUPAN, Henning
Publication of US20170320128A1 publication Critical patent/US20170320128A1/en
Abandoned legal-status Critical Current

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22CFOUNDRY MOULDING
    • B22C1/00Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
    • B22C1/18Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of inorganic agents
    • B22C1/186Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of inorganic agents contaming ammonium or metal silicates, silica sols
    • B22C1/188Alkali metal silicates
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22CFOUNDRY MOULDING
    • B22C9/00Moulds or cores; Moulding processes
    • B22C9/02Sand moulds or like moulds for shaped castings
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22CFOUNDRY MOULDING
    • B22C9/00Moulds or cores; Moulding processes
    • B22C9/10Cores; Manufacture or installation of cores
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/02Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B28WORKING CEMENT, CLAY, OR STONE
    • B28BSHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B1/00Producing shaped prefabricated articles from the material
    • B28B1/001Rapid manufacturing of 3D objects by additive depositing, agglomerating or laminating of material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B28WORKING CEMENT, CLAY, OR STONE
    • B28BSHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B11/00Apparatus or processes for treating or working the shaped or preshaped articles
    • B28B11/24Apparatus or processes for treating or working the shaped or preshaped articles for curing, setting or hardening
    • B28B11/241Apparatus or processes for treating or working the shaped or preshaped articles for curing, setting or hardening using microwave heating means
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00Moulds or cores; Details thereof or accessories therefor
    • B29C33/38Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process
    • B29C33/3807Resin-bonded materials, e.g. inorganic particles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00Moulds or cores; Details thereof or accessories therefor
    • B29C33/44Moulds or cores; Details thereof or accessories therefor with means for, or specially constructed to facilitate, the removal of articles, e.g. of undercut articles
    • B29C33/448Moulds or cores; Details thereof or accessories therefor with means for, or specially constructed to facilitate, the removal of articles, e.g. of undercut articles destructible
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00Moulds or cores; Details thereof or accessories therefor
    • B29C33/44Moulds or cores; Details thereof or accessories therefor with means for, or specially constructed to facilitate, the removal of articles, e.g. of undercut articles
    • B29C33/54Moulds or cores; Details thereof or accessories therefor with means for, or specially constructed to facilitate, the removal of articles, e.g. of undercut articles made of powdered or granular material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10Processes of additive manufacturing
    • B29C64/141Processes of additive manufacturing using only solid materials
    • B29C64/153Processes of additive manufacturing using only solid materials using layers of powder being selectively joined, e.g. by selective laser sintering or melting
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10Processes of additive manufacturing
    • B29C64/165Processes of additive manufacturing using a combination of solid and fluid materials, e.g. a powder selectively bound by a liquid binder, catalyst, inhibitor or energy absorber
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B18/00Layered products essentially comprising ceramics, e.g. refractory products
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE 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
    • B33Y10/00Processes of additive manufacturing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE 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
    • B33Y50/00Data acquisition or data processing for additive manufacturing
    • B33Y50/02Data acquisition or data processing for additive manufacturing for controlling or regulating additive manufacturing processes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE 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
    • B33Y70/00Materials specially adapted for additive manufacturing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE 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
    • B33Y80/00Products made by additive manufacturing
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/14Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silica
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/6303Inorganic additives
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/6303Inorganic additives
    • C04B35/6306Binders based on phosphoric acids or phosphates
    • C04B35/6313Alkali metal or alkaline earth metal phosphates
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/6303Inorganic additives
    • C04B35/6316Binders based on silicon compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J1/00Adhesives based on inorganic constituents
    • C09J1/02Adhesives based on inorganic constituents containing water-soluble alkali silicates
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3201Alkali metal oxides or oxide-forming salts thereof
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3409Boron oxide, borates, boric acids, or oxide forming salts thereof, e.g. borax
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3427Silicates other than clay, e.g. water glass
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54Particle size related information
    • C04B2235/5418Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5427Particle size related information expressed by the size of the particles or aggregates thereof millimeter or submillimeter sized, i.e. larger than 0,1 mm
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54Particle size related information
    • C04B2235/5418Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5436Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
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    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/60Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/602Making the green bodies or pre-forms by moulding
    • C04B2235/6026Computer aided shaping, e.g. rapid prototyping
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    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/66Specific sintering techniques, e.g. centrifugal sintering
    • C04B2235/667Sintering using wave energy, e.g. microwave sintering
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    • C04B2237/00Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/50Processing aspects relating to ceramic laminates or to the joining of ceramic articles with other articles by heating
    • C04B2237/70Forming laminates or joined articles comprising layers of a specific, unusual thickness
    • C04B2237/704Forming laminates or joined articles comprising layers of a specific, unusual thickness of one or more of the ceramic layers or articles
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/25Process efficiency

Definitions

  • the invention relates to a method for constructing molds and cores layer by layer, the molds and cores comprising a refractory molding base material and a binder containing least one aqueous alkali silicate solution and further a phosphate or a borate or both.
  • a refractory molding base material In order to produce molds and cores layer by layer in 3-D printing it is necessary to apply a refractory molding base material layer by layer and to selectively print each with the binder.
  • the invention relates to molds or cores produced in this way.
  • Casting molds essentially consist of cores and molds, which represent the negative forms of the casting to be produced.
  • These cores and molds consist of a refractory material, for example quartz sand, and a suitable binder which imparts sufficient mechanical strength to the casting mold after removal from the forming die.
  • a refractory molding base material is used, which is coated with a suitable binder.
  • the refractory molding base material is preferably in a free-flowing form so that it can be filled into a suitable hollow mold.
  • the binder creates a firm cohesion between the particles/granules of the molding base material so that the casting mold is given the required mechanical stability.
  • Casting molds have to meet various requirements. In the casting process itself, they firstly have to have sufficient stability and heat resistance to accommodate the liquid metal in the hollow space formed by one or more (parts of) casting molds. After commencement of solidification, the mechanical stability of the casting mold is ensured by a solidified metal layer which forms along the walls of the casting mold. The material of the casting mold then has to decompose under the action of the heat given off by the metal so that it loses its mechanical strength, i. e. cohesion between individual particles/granules of the refractory material is lost. In the ideal case the casting mold disintegrates again to leave a fine sand which can be poured from the casting mold of the casting.
  • rapid prototyping includes various known methods for the production of three-dimensional bodies by constructing them layer by layer.
  • An advantage of these methods is the possibility of producing even complex single-piece bodies with undercuts and cavities. By conventional methods these bodies would have to be assembled from several, individually produced parts.
  • a further advantage is that the methods are capable of producing the bodies without molding dies directly from the CAD data.
  • binders which hold the casting mold together when the binder or a binder component is to be applied through the nozzles of a print head.
  • the binders must then not only lead to a sufficient strength level and to good disintegration properties after the metal casting, and also have sufficient thermal and storage stability, but also now must be “printable”, that is, the nozzles of the print head can not be blocked by the binder, on the other hand, the binder should also not be able to flow directly out of the print head but instead form single droplets.
  • EP 1802409 B1 discloses an inorganic binder system with which it is possible to produce molds with sufficient stability.
  • the binder system is particularly suitable for thermal curing in a core firing machine in which a previously mixed molding material mixture (mixture of refractory material and binder) is conveyed into the heated molding die by means of pressure.
  • WO 2012/175072 A1 discloses a method for constructing models layer by layer, wherein an inorganic binder system is used.
  • the particulate material applied layer by layer comprises a particulate construction material and a spray-dried alkali silicate solution.
  • the selective activation of the curing is carried out by means of a solution comprising water, which is added by means of the print head.
  • Both pure water and modified water containing rheological additives are disclosed.
  • Rheological additives mentioned are exemplified by thickening agents, such as glycerol, glycol or layered silicates, the layered silicates being particularly emphasized.
  • WO 2012/175072 A1 does not disclose the use of aqueous alkali silicate solutions.
  • the binder or the water-glass solution is not dosed via the print head, but is already contained in the particulate material applied layer by layer.
  • the selective wetting or setting of a material applied layer by layer by means of a binder is achieved according to WO 2012/175072 A1 only by a detour and not directly by means of an aqueous alkali silicate solution.
  • the process described in WO 2012/175072 A1 provides the binder, the spray-dried alkali silicate solution, not only at the intended destination, but also in areas in which it is not required. Thus, the binder is consumed unnecessarily.
  • DE 102011053205 A1 discloses a method for producing a component in deposition technology in which, inter alia, water glass is used as a printing liquid in addition to many other options. Accordingly, the water glass can be dosed by means of a print head and applied to a predetermined section of the respectively uppermost layer.
  • DE 102011053205 A1 does not provide information as to which water glass compositions can be used. The person skilled in the art is also not given any information about the physical properties of the water glasses used, which could have indicated a chemical composition.
  • inorganic binders such as, e. g., free-flowing water glass
  • inorganic binders are mentioned quite generally, which generally contain large amounts of moisture—as an example, only up to 60% by weight water is mentioned. The large amounts of water (e. g. up to 60% by weight water) are thought to be disadvantageous since they are difficult to handle.
  • WO 2013/017134 A1 discloses an aqueous alkali silicate solution having a viscosity of 45 mPa ⁇ s or less at 20° C., which has a solids content with respect to the alkali silicate of 39% by weight.
  • the ratio between SiO 2 and M 2 O is stated as the weight ratio.
  • the narrowest limits of this weight ratio are between 1.58 and 3.30.
  • W02013/017134 A1 a method is disclosed with which it appears possible to lower the viscosity of water glass binders by means of a ball mill. However, such a method is very complex and cost-intensive.
  • the inventors are therefore faced with the object of developing a water glass binder or an aqueous alkali silicate solution which is suitable for the 3-dimensional printing of casting molds, i. e., the water glass binder can be selectively dosed directly via a print head without blocking or clogging the nozzles or the module of the print head. Furthermore, the binder should be applied as finely, punctiformly and in a precisely defined dose. Moreover, the use of the water glass according to the invention leads to positive properties of the molds produced therewith.
  • the method for constructing bodies layer by layer comprises at least the following steps:
  • the casting molds produced therewith have the following properties:
  • the binder according to the invention is very readily “printable”, that is to say the nozzles of the printing head are not rapidly blocked by the binder. At the same time, the binder can be applied very finely. A clogging of the nozzles of the print head would lead to a poor print result. This is avoided by the binder according to the invention.
  • a rapid clogging of the nozzles or a rapid film formation at the module of the print head is due to an increased reactivity of the binder.
  • the reactivity of the binder can be controlled by its chemical composition as well as the thermal stability of the binder.
  • a low reactivity of the binder is required in order to avoid impairment of the print head and to control the curing of the binder, but on the other hand, high thermal stability is desired also in order to prevent the produced casting molds from deforming during the casting operation and thus resulting in poor dimensional stability of the casting.
  • the thermostability and reactivity of the binder depend in the same manner on the chemical composition of the binder, i. e., the higher the reactivity, the higher the thermal stability. It is the subject matter of this invention to disclose a suitable binder composition which ensures a sufficiently high thermostability of the casting molds at sufficiently low reactivity of the binder.
  • the binder according to the invention is provided for the 3-dimensional printing of casting molds.
  • the binder serves as a printing liquid, by means of which a material applied layer by layer, such as, for example, a refractory molding base material (e. g. quartz sand) and optionally one or more additives, collectively referred to as a construction material mixture, is selectively printed.
  • a material applied layer by layer such as, for example, a refractory molding base material (e. g. quartz sand) and optionally one or more additives, collectively referred to as a construction material mixture.
  • the construction material mixture does not yet contain the binder.
  • a selective printing operation follows the layer by layer application of the construction material mixture—this operation is repeated until the entire printing operation is completed and the casting mold can be obtained.
  • the curing of the binder can be carried out in conventional ways.
  • thermal curing can also take place. It is, for example, possible for thermal curing to be carried out after completion of a printing operation (immediately before, during or after the next layer of the construction material mixture is applied), by irradiating the mixture of construction material mixture and binding agent, for example, by means of an infrared light. In this layer by layer curing, the infrared light, for example in the form of a spot, can follow the print head.
  • thermal curing step by step after several layers have been applied. It is also possible to carry out the thermal curing only after completion of the last printing operation.
  • the steps “applying a layer of the construction material mixture” and subsequent “printing operation” alternate until the last layer has been printed which is necessary to produce the casting mold completely. For this purpose, the applied and partially printed layers remain, for example in a so-called “job box”, which subsequently can be transferred to a microwave oven to perform thermal curing.
  • Thermal curing is preferred, in particular drying by means of microwaves and preferably after completion of the entire printing operation in the microwave oven.
  • Customary and known materials can be used as the refractory molding base materials for the production of casting molds.
  • Suitable materials are, for example, quartz, zirconium or chromium ore sand, olivine, vermiculite, bauxite, fire clay as well as artificial molding base materials, in particular more than 50% by weight quartz sand based on the refractory molding base material.
  • the proportion of quartz sand of the refractory molding base material is greater than 70% by weight, preferably greater than 80% by weight and particularly preferably greater than 90% by weight. It is not necessary, however, to use exclusively new sands. In the sense of saving resources and avoiding landfill costs, it is even advantageous to use as high a proportion of regenerated old sand as is obtainable from used forms by recycling.
  • a refractory molding base material is understood to mean substances which have a high melting point (melting temperature).
  • the melting point of the refractory molding base material is preferably greater than 600° C., preferably greater than 900° C., particularly preferably greater than 1200° C. and very particularly preferably greater than 1500° C.
  • the refractory molding base material preferably makes up greater than 80% by weight, in particular greater than 90% by weight, particularly preferably greater than 95% by weight, of the construction material mixture.
  • regenerates which are obtainable by washing and subsequent drying of comminuted used molds.
  • the regenerates can make up 70% by weight of the refractory molding base material, preferably at least about 80% by weight and particularly preferably greater than 90% by weight.
  • regenerates which have been obtained by purely mechanical treatment.
  • a mechanical treatment is understood to mean that at least a portion of the binder remaining in the old sand is removed from the sand grain by a grinding or impacting principle.
  • regenerates can be used as needed.
  • the proportion of these regenerates can, for example, be greater than 5% by weight, preferably greater than 20% by weight, more preferably greater than 50% by weight, particularly preferably greater than 70% by weight and very particularly preferably greater than 80% by weight, of the refractory molding base material.
  • Such regenerates are used, for example, to effect a (pre- or partial) curing of the applied binder.
  • salts are understood to mean alkali halides and alkaline earth halides. Alkali halides are preferred, of which the alkali metal chlorides are more preferred. Particularly preferably, sodium chloride is used.
  • the proportion of the salts or the salt can make up, for example, greater than 5% by weight, preferably greater than 20% by weight, more preferably greater than 50% by weight, more preferably greater than 80% by weight, of the refractory molding base material. It is particularly preferred in this embodiment to use only the salt as a refractory molding base material. Salts are used, for example, when the casting mold is to be removed after the metal casting by means of water.
  • the mean grain diameter of the refractory molding base material is generally between 50 ⁇ m and 600 ⁇ m, preferably between 70 ⁇ m and 400 ⁇ m, preferably between 80 ⁇ m and 300 ⁇ m, and particularly preferably between 100 ⁇ m and 200 ⁇ m.
  • the grain diameter can be determined, for example, by sieving according to DIN ISO 3310.
  • Particularly preferred are particle shapes/grains having the greatest longitudinal extent to the smallest longitudinal extent (at right angles to one another and in each case for all spatial directions) of 1:1 to 1:5 or 1:1 to 1:3, i. e., those which are non-fibrous, for example.
  • the refractory molding base material is in a free-flowing state.
  • the binder according to the invention contains water glasses which are prepared, for example, by dissolving glassy lithium, sodium and/or potassium silicates in water.
  • Preferred water glasses are those which contain at least sodium silicates.
  • the ratio Na 2 O/M 2 O in the binder is preferably greater than 0.4, preferably greater than 0.5 and more preferably greater than 0.6 and particularly preferably greater than 0.7, wherein M 2 O is the sum of the mass quantities of lithium, sodium and potassium calculated as oxide in the binder.
  • the amounts of the alkali metals are calculated exclusively from the molar amounts of amorphous alkali silicates, alkali oxides, alkali hydroxides, alkali phosphates and alkali borates present in the binder. This means that any additions such as alkali chloride or alkali carbonates to the water glass solution are not included in the calculation of M 2 O (M 2 O in each case as defined in the previous paragraph).
  • the water glass has a molar modulus SiO 2 /M 2 O of greater than 1.4, preferably greater than 1.6, preferably greater than 1.8, more preferably greater than 1.9, and particularly preferably greater than 2.0.
  • the water glass preferably has a molar modulus SiO 2 /M 2 O of less than 2.8, preferably less than 2.6, preferably less than 2.5, particularly preferably less than 2.4.
  • molar modulus SiO 2 /M 2 O of the water glass solutions according to the invention lead to a sufficiently high thermostability of the casting mold, in particular in metal casting.
  • the binder has a solids content of less than 40% by weight, preferably less than 38% by weight, preferably less than 36% by weight, particularly preferably less than 35% by weight.
  • the remainder of the binder preferably consists of water.
  • the binder has a solids content of greater than 22% by weight, preferably greater than 24% by weight, preferably greater than 26% by weight, particularly preferably greater than 28% by weight, very particularly preferably greater than 29% by weight and particularly preferably greater than 29.5%.
  • the solids content is determined by gently evaporating the liquid, drying the binder and then heating it at 600° C. for 1 h in an air atmosphere. The remaining oxidic material is weighed to determine the solids content.
  • the amount of material of SiO 2 and M 2 O (calculated as mol %) in the binder is less than 16 mol %, preferably less than 15 mol %, preferably less than 14 mol %, particularly preferably less than 13.5 mol %. Furthermore, this amount of material is greater than 7 mol %, preferably greater than 8 mol %, preferably greater than 9 mol %, particularly preferably greater than 10 mol % and very particularly preferably greater than 10.5 mol %.
  • the viscosity of the binder must not be too low and not too high.
  • the dynamic viscosity is measured using a Brookfield rotation viscometer.
  • the binder according to the invention has a viscosity of less than 25 mPas, preferably less than 20 mPas, preferably less than 18 mPas, and particularly preferably less than 16 mPas.
  • the binder has a viscosity of greater than 1 mPas, preferably greater than 2 mPas, preferably greater than 3 mPas, and particularly preferably greater than 4 mPas.
  • the binder according to the invention should be a clear solution and, if possible, free of coarser particles, which in their greatest extent have a size between several micrometers to several millimeters and can originate, for example, from impurities. Commercially available water glass solutions generally have these coarser particles.
  • Particle or grain sizes are determined by means of dynamic light scattering in accordance with DIN/ISO 13320 (e. g. Horiba LA 950).
  • the determined D90 value (in each case based on volume) is the measure for the larger particles—it means that 90% of the particles are smaller than the specified value.
  • the water glass according to the invention has a D90 value (determined by dynamic light scattering or laser diffractometry) of less than 70 ⁇ m, preferably less than 40 ⁇ m, preferably less than 30 ⁇ m, particularly preferably less than 25 ⁇ m, and very particularly preferably less than 20 ⁇ m.
  • the water glass according to the invention has a D100 value (in each case based on volume) of less than 250 ⁇ m, preferably less than 120 ⁇ m, preferably less than 50 ⁇ m, more preferably less than 40 ⁇ m, particularly preferably less than 35 ⁇ m, and very particularly preferably less than 30 ⁇ m.
  • the binders described above containing water glasses can be obtained, for example, by suitable filtration.
  • filters with a sieve diameter of 50 ⁇ m, preferably of 25 ⁇ m, preferably 10 ⁇ m, and particularly preferably 5 ⁇ m, are suitable.
  • Preferred binders are those which contain no particles with a size of at least 1 ⁇ m.
  • the binder according to the invention can have proportions of lithium ions.
  • the molar ratio of Li 2 O/M 2 O can vary over wide ranges, for example between 0.01 and 0.3. Preferably, the ratio is in the range between 0.03 and 0.17, preferably between 0.035 and 0.16, and particularly preferably between 0.04 and 0.14.
  • the binder according to the invention can have proportions of potassium ions.
  • the molar ratio of K 2 O/M 2 O can vary over wide ranges, for example between 0.01 and 0.3. Preferably, the ratio is in the range between 0.01 and 0.17, preferably between 0.02 and 0.16 and particularly preferably between 0.03 and 0.14.
  • alkali phosphates e. g. sodium hexametaphosphate or sodium polyphosphates
  • alkali phosphates e. g. sodium hexametaphosphate or sodium polyphosphates
  • alkali orthophosphates such as trisodium phosphate (Na 3 PO 4 ) are not preferred.
  • Sodium polyphosphates and/or sodium metaphosphates are particularly preferred.
  • borates in particular alkali borates, e. g., disodium tetraborate decahydrate. These, too, are dissolved in the binder.
  • the amounts of the alkali metals which result from the proportions of the alkali borates and/or alkali phosphates in the total amount of the binder (including diluent) are calculated as oxides and contribute to the total amount of material (i. e. the sum of the individual amounts of material) of lithium, sodium and potassium oxide in the total aqueous solution. Consequently, the molar modulus SiO 2 /M 2 O is also influenced by the addition of alkali borates and/or alkali phosphates.
  • the content of borates in the binder is calculated as B 2 O 3 .
  • the molar ratio of B 2 O 3 /SiO 2 can vary over wide ranges, for example from 0 to 0.5. This ratio is preferably less than 0.3, preferably less than 0.2, particularly preferably less than 0.1, very particularly preferably less than 0.08 and most particularly preferably less than 0.06. Preferably, this ratio is greater than or equal to zero. In a further embodiment, this ratio is preferably greater than 0.01, particularly preferably greater than 0.02.
  • Borates in the context of the invention are boron compounds in the oxidation state III, which are only directly bonded to oxygen, i. e., oxygen atoms are the direct bonding partners of the boron in the compound.
  • the content of phosphates in the binder is calculated as P 2 O 5 .
  • the molar ratio of P 2 O 5 /SiO 2 can vary over wide ranges, for example from 0 to 0.5. This ratio is preferably less than 0.4, preferably less than 0.3, more preferably less than 0.25, particularly preferably less than 0.2 and very particularly preferably less than 0.15. This ratio is preferably greater than 0, preferably greater than 0.01, particularly preferably greater than 0.02.
  • Phosphates in the context of the invention are phosphorus compounds in the oxidation state V, which are only directly bonded to oxygen, i. e. oxygen atoms are the direct bonding partners of the phosphorus in the compound.
  • the binder can also contain aluminum, wherein the proportion of the aluminum being then calculated as Al 2 O 3 .
  • the proportion of Al 2 O 3 is then usually less than 2% by weight, based on the total weight of the binder.
  • surface-active substances may be added to the binder according to the invention in order to influence the surface tension of the binder.
  • the proportion of these surface-active substances is generally between 0.01 and 4.0% by weight, preferably between 0.1 and 3.0% by weight.
  • Suitable surface-active substances in the binder are, for example, described in DE 102007051850 A1, including preferably anionic surfactants which carry a sulfate and/or sulfonate group.
  • Further suitable surface-active substances are, for example, polyacrylate salts (e. g. of sodium—for example Dispex N40-Ciba) or silicone surfactants for aqueous systems (e. g. Byk 348, Altana).
  • Surface-active substances based on trisiloxane or glycol e. g. polyethylene glycol
  • binder based on the water glass
  • preferably between 0.5% by weight and 7% by weight of binder, based on the water glass is used, preferably between 0.75% by weight and 6% by weight, particularly preferably between 1% by weight and 5.0% by weight, and particularly preferably between 1% by weight and 4.0% by weight, based in each case on the molding base material.
  • the construction material mixture may contain a proportion of a particulate amorphous silica to enhance the strength level of the casting molds.
  • a particulate amorphous silica to enhance the strength level of the casting molds.
  • An increase in the strengths of the casting molds, in particular the increase in the hot strengths, can be advantageous in the automated production process. Synthetically produced amorphous silica is particularly preferred.
  • the mean particle size (including any agglomerates) of the amorphous silica is preferably less than 300 ⁇ m, preferably less than 200 ⁇ m, particularly preferably less than 100 ⁇ m.
  • the sieve residue of the particulate amorphous SiO 2 is preferably not more than 10% by weight, particularly preferably not more than 5% by weight, and very particularly preferably not more than 2% by weight, when passing through a sieve of 125 ⁇ m mesh (120 mesh).
  • the sieve residue on a sieve with 63 ⁇ m mesh is less than 10% by weight, preferably less than 8% by weight.
  • the sieve residue is determined according to the machine sieving method described in DIN 66165 (part 2), in which case a chain ring is additionally used as sieving aid.
  • the particulate amorphous silicon dioxide preferably used according to the present invention has a water content of less than 15% by weight, in particular less than 5% by weight and particularly preferably less than 1% by weight.
  • the particulate amorphous SiO 2 is used as a powder (including dusts).
  • amorphous SiO 2 Both synthetically produced and naturally occurring silicic acids can be used as amorphous SiO 2 .
  • the latter are known, for example, from DE 102007045649, but are not preferred, since they usually contain not insignificant crystalline proportions and are therefore classified as carcinogens.
  • Synthetic is understood to mean non-naturally occurring amorphous SiO 2 , i. e., its preparation comprises a deliberately performed chemical reaction, as is caused by a human, e. g. the production of silica sols by ion exchange processes from alkali silicate solutions, the precipitation from alkali silicate solutions, the flame hydrolysis of silicon tetrachloride, the reduction of quartz sand with coke in the arc furnace in the production of ferrosilicon and silicon.
  • the amorphous SiO 2 produced by the two last-mentioned methods is also referred to as pyrogenic SiO 2 .
  • Precipitated silicic acids and pyrogenic, i. e., silicon dioxide produced by flame hydrolysis or in the electric arc are used preferably.
  • Amorphous silicon dioxide (described in DE 102012020509) produced by thermal decomposition of ZrSiO 4 and SiO 2 (described in DE 102012020510) produced by oxidation of metallic Si by means of an oxygen-containing gas are used particularly preferably.
  • Quartz glass powder (mainly amorphous silicon dioxide), which has been produced by melting and rapid re-cooling from crystalline quartz, so that the particles are spherical and not splintered (described in DE 102012020511) are also preferred.
  • the mean primary particle size of the particulate amorphous silicon dioxide can be between 0.05 ⁇ m and 10 ⁇ m, in particular between 0.1 ⁇ m and 5 ⁇ m, particularly preferably between 0.1 ⁇ m and 2 ⁇ m.
  • the primary particle size can be determined, e. g., by means of dynamic light scattering (e. g. Horiba LA 950) as well as by scanning electron micrographs (SEM images with, e. g., Nova NanoSEM 230 from FEI). Furthermore, details of the primary particle shape could be visualized up to the order of 0.01 ⁇ m using the SEM images.
  • the silicon dioxide samples were dispersed in distilled water for the SEM measurements and then applied to an aluminum holder bonded with copper tape before the water was evaporated.
  • the specific surface area of the particulate amorphous silicon dioxide was determined by means of gas adsorption measurements (BET method) according to DIN 66131.
  • the specific surface area of the particulate amorphous SiO 2 is between 1 and 200 m 2 /g, in particular between 1 and 50 m 2 /g, particularly preferably between 1 and 30 m 2 /g.
  • the products can also be blended, e. g., in order to obtain mixtures with specific particle size distributions.
  • the purity of the amorphous SiO 2 can vary widely. Suitable types have a silicon dioxide content of at least 85% by weight, preferably at least 90% by weight and particularly preferably at least 95% by weight.
  • the particulate amorphous SiO 2 are used, preferably between 0.1% by weight and 1.8% by weight, particularly preferably between 0.1% by weight and 1.5% by weight, based in each case on the molding base material.
  • the ratio of water glass-based binder to particulate amorphous silicon dioxide can be varied within wide limits.
  • the amorphous SiO 2 is preferably present in a proportion from 1 to 80% by weight, preferably from 2 to 60% by weight, particularly preferably from 3 to 55% by weight and very particularly preferably from 4 to 50% by weight. Or Irrespective of this, based on the ratio of the proportion of solids of the water glass-based binder (based on the oxides, i. e., the total mass of alkali metal oxides M 2 O and silicon dioxide) to amorphous SiO 2 of 10:1 to 1:1.2 (weight parts) preferred.
  • the amorphous SiO 2 is added to the refractory solid or to the construction material mixture prior to the addition of the binder.
  • the method according to the invention is furthermore characterized by one or more of the following features when using amorphous SiO 2 :
  • the amorphous silicon dioxide has a BET surface area between 1 and 200 m 2 /g, preferably greater than or equal to 1 m 2 /g and less than or equal to 30 m 2 /g, particularly preferably less than or equal to 15 m 2 /g.
  • the amorphous silica is selected from the group consisting of precipitated silicic acid, pyrogenic silicon dioxide produced by flame hydrolysis or in the electric arc, amorphous silicon dioxide produced by flame decomposition of ZrSiO 4 , silicon dioxide produced by oxidation of metallic silicon by means of an oxygen-containing gas, quartz glass powder having spherical particles produced by melting and rapid re-cooling of crystalline quartz, and mixtures thereof, and is preferably amorphous silicon dioxide produced by thermal decomposition of ZrSiO 4 .
  • the amorphous silicon dioxide is preferably used in amounts of 0.1 to 2% by weight, particularly preferably 0.1 to 1.5% by weight, based in each case on the refractory molding base material.
  • the amorphous silicon dioxide has a water content of less than 5% by weight and particularly preferably less than 1% by weight.
  • the amorphous silicon dioxide is particulate amorphous silicon dioxide, preferably with a mean primary particle diameter determined by dynamic light scattering between 0.05 ⁇ m and 10 ⁇ m, in particular between 0.1 ⁇ m and 5 ⁇ m, and particularly preferably between 0.1 ⁇ m and 2 ⁇ m.
  • an inorganic curing agent for water glass-based binders is added to the construction material mixture prior to the addition of the binder.
  • Such inorganic curing agents are, e. g., phosphates such as, for example, Lithopix P26 (an aluminum phosphate from Zschimmer and Schwarz GmbH & Co KG Chemsche Fabriken) or Fabutit 748 (an aluminum phosphate from Chemische Fabrik Budenheim KG).
  • Other inorganic curing agents for water glass-based binders are, for example, calcium silicates and their hydrates, calcium aluminates and their hydrates, aluminum sulfate, magnesium and calcium carbonate.
  • the ratio of curing agent to binder may vary depending on the desired property, e.g. processing time and/or dismantling time of the construction material mixtures.
  • the curing agent proportion (weight ratio of curing agent to binder and in the case of water glass the total weight of the silicate solution or other binders incorporated in solvents) is greater than or equal to 5% by weight, preferably greater than or equal to 8% by weight, particularly preferably greater than or equal to 10% by weight, based in each case on the binder.
  • the upper limits are less than or equal to 25% by weight, based on the binder, preferably less than or equal to 20% by weight, particularly preferably less than or equal to 15% by weight.
  • the inorganic curing agent between 0.05% by weight and 2% by weight are used, preferably between 0.1% by weight and 1% by weight, particularly preferably between 0.1% by weight and 0.6% by weight, based in each case on the molding base material.
  • the unbonded construction material mixture can then be removed from the casting mold and the casting mold fed to the further treatment, for example, the preparation for metal casting.
  • the removal of the unbonded from the bonded construction material mixture is achieved, for example, by means of an outlet so that the unbonded construction material mixture can trickle out.
  • the bonded construction material mixture (casting mold) can, for example, be freed from residues of the unbonded construction material mixture by means of compressed air or by brushing.
  • the unbonded construction material mixture can be re-used for a new printing operation.
  • Printing is carried out, e. g., with a print head having a plurality of nozzles, the nozzles preferably being individually selectively controllable.
  • the print head is moved in at least one plane controlled by a computer, and the nozzles apply the liquid binder layer by layer.
  • the print head can be, e. g., a drop-on-demand print head with bubble-jet or preferably piezo technology.

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Publication number Priority date Publication date Assignee Title
RU2696590C1 (ru) * 2018-11-14 2019-08-06 Федеральное государственное бюджетное образовательное учреждение высшего образования "Чувашский государственный университет имени И.Н. Ульянова" Способ приготовления жидкостекольного связующего для получения формовочных и стержневых смесей
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US10981215B2 (en) * 2017-06-30 2021-04-20 HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung Method for producing a moulding material mixture and a moulded body thereof in the casting industry and kit for use in this method
US11104029B2 (en) * 2016-02-26 2021-08-31 Hewlett-Packard Development Company, L.P. Three-dimensional (3D) printing
US11123789B2 (en) * 2019-01-22 2021-09-21 Lift Technology Method for inorganic binder castings
US11179768B2 (en) * 2018-05-28 2021-11-23 Abb Sp. Z O.O Method of preparation of sand casting moulds with a protective coating
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Publication number Priority date Publication date Assignee Title
DE102016124061A1 (de) 2016-12-12 2018-06-14 KTM Technologies GmbH Verlorener Formkern sowie ein Verfahren zur Herstellung eines Bauteils und das Bauteil selbst
DE102017107531A1 (de) * 2017-04-07 2018-10-11 HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung Verfahren zur Herstellung von Gießformen, Kernen und daraus regenerierten Formgrundstoffen
WO2018210437A1 (de) 2017-05-16 2018-11-22 Idee & Design The Art Factory Gmbh Verfahren und vorrichtung zur herstellung eines dreidimensionalen objekts
WO2018215113A1 (de) * 2017-05-23 2018-11-29 Exone Gmbh NACHBEHANDLUNGSVERFAHREN ZUR ERHÖHUNG DER HEIßFESTIGKEIT EINES AUS PARTIKELMATERIAL UND BINDEMITTEL GEFERTIGTEN FORMTEILS, 3D-DRUCK-ANORDNUNG UND FORMTEIL
KR102022258B1 (ko) * 2017-10-23 2019-09-18 한국도자기주식회사 바인더 제팅 3d 프린팅용 도자기 조성물 및 이를 이용한 도자기의 제조방법
CN108102555A (zh) * 2017-12-27 2018-06-01 杜海芳 一种无机耐高温粘结组合物及制备方法与应用
DE102018200607A1 (de) 2018-01-15 2019-07-18 Reinsicht Gmbh Verfahren zur Erzeugung von für die Herstellung von Faserverbundkörpern oder Gussteilen aus Metall oder Kunststoff geeigneten Formen und Kernen, bei dem Verfahren einsetzbare Formgrundstoffe und Binder sowie gemäß dem Verfahren hergestellte Formen und Kerne
DE102018111014B4 (de) 2018-05-08 2023-03-30 Ernst-Abbe-Hochschule Jena Verfahren zum dreidimensionalen additiven Aufbau eines Formkörpers aus Wasserglas
DE102018131811A1 (de) 2018-08-13 2020-02-13 HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung Verwendung einer Schlichtezusammensetzung und entsprechendes Verfahren zur Herstellung einer Schleudergusskokille mit einem Schlichteüberzug
JP7156096B2 (ja) * 2019-03-06 2022-10-19 新東工業株式会社 付加製造システム及び容器
EP3747634B1 (de) * 2019-06-07 2022-05-04 ExOne GmbH Verfahren zum herstellen mindestens eines bauteils im 3d-druck und 3d-drucker
DE102019116406A1 (de) 2019-06-17 2020-12-17 HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung Additivmischung für Formstoffmischungen zur Herstellung wasserglasgebundener Gießereiformen und Gießereikerne
DE102019116702A1 (de) * 2019-06-19 2020-12-24 Ask Chemicals Gmbh Geschlichtete Gießformen erhältlich aus einer Formstoffmischung enthaltend ein anorganisches Bindemittel und Phosphat- und oxidische Borverbindungen, ein Verfahren zu deren Herstellung und deren Verwendung
DE102020102784A1 (de) 2019-11-17 2021-05-20 Fricke Und Mallah Microwave Technology Gmbh Mikrowellen-sandformkasten
CN110819167A (zh) * 2019-11-25 2020-02-21 武汉绿之美铸造材料有限公司 一种喷墨式的3d打印机用墨水及其制造方法
DE102020107742A1 (de) 2020-03-20 2021-09-23 Bayerische Motoren Werke Aktiengesellschaft Verfahren zur Herstellung eines Formkörpers
DE102020110289A1 (de) 2020-04-15 2021-10-21 Peak Deutschland Gmbh Verfahren unter Verwendung eines anorganischen Binders für die Herstellung von ausgehärteten dreidimensional geschichteten Formkörpern für Gießereikerne und -formen
WO2021262172A1 (en) * 2020-06-25 2021-12-30 Hewlett-Packard Development Company, L.P. Shear thinning build material slurry
DE102020119013A1 (de) 2020-07-17 2022-01-20 HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung Verfahren zur Herstellung eines Artikels zur Verwendung in der Gießereiindustrie, entsprechende Form, Kern, Speiserelement oder Formstoffmischung sowie Vorrichtungen und Verwendungen
KR102595277B1 (ko) * 2021-03-25 2023-10-27 한국생산기술연구원 3d 프린팅용 무기 바인더 및 그 제조방법
DE102021002770A1 (de) * 2021-05-28 2022-12-01 Voxeljet Ag 3d-druckverfahren und damit hergestelltes formteil unter verwendung von wasserglasbinder und ester
DE102021116930A1 (de) 2021-06-30 2023-01-05 Ask Chemicals Gmbh Verfahren zum schichtweisen aufbau von formen und kernen mit einem wasserglashaltigen bindemittel
AT525545B1 (de) * 2021-10-27 2023-05-15 Breitenberger Georg Verfahren und vorrichtung zur herstellung von formbauteilen

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4233078A (en) * 1979-07-03 1980-11-11 Kaiser Aluminum & Chemical Corporation Refractory composition for forming a monolithic structure
US6139619A (en) * 1996-02-29 2000-10-31 Borden Chemical, Inc. Binders for cores and molds
US7381360B2 (en) * 2003-11-03 2008-06-03 Hewlett-Packard Development Company, L.P. Solid free-form fabrication of three-dimensional objects
US7807077B2 (en) * 2003-06-16 2010-10-05 Voxeljet Technology Gmbh Methods and systems for the manufacture of layered three-dimensional forms
US20100326620A1 (en) * 2007-10-30 2010-12-30 Ashland-Südchemie-Kernfest GmbH Mould material mixture having improved flowability

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4347890A (en) * 1981-03-09 1982-09-07 Pq Corporation Method for binding particulate materials
EP0111398B1 (de) * 1982-12-11 1987-01-21 Foseco International Limited Bindemittelzusammensetzungen auf der Basis von Alkalimetallsilikat
JP2618448B2 (ja) 1988-08-09 1997-06-11 株式会社日立製作所 ガスタービン燃焼器状態監視装置及び監視方法及び制御方法
US5204055A (en) * 1989-12-08 1993-04-20 Massachusetts Institute Of Technology Three-dimensional printing techniques
WO1995032824A1 (de) * 1994-05-27 1995-12-07 Eos Gmbh Electro Optical Systems Verfahren für den einsatz in der giessereitechnik
SE520565C2 (sv) * 2000-06-16 2003-07-29 Ivf Industriforskning Och Utve Sätt och apparat vid framställning av föremål genom FFF
US8741194B1 (en) 2000-09-25 2014-06-03 Voxeljet Ag Method for producing a part using a depostion technique
US7087109B2 (en) * 2002-09-25 2006-08-08 Z Corporation Three dimensional printing material system and method
DE102004042535B4 (de) 2004-09-02 2019-05-29 Ask Chemicals Gmbh Formstoffmischung zur Herstellung von Gießformen für die Metallverarbeitung, Verfahren und Verwendung
DE102006049379A1 (de) 2006-10-19 2008-04-24 Ashland-Südchemie-Kernfest GmbH Phosphorhaltige Formstoffmischung zur Herstellung von Giessformen für die Metallverarbeitung
DE102007008149A1 (de) 2007-02-19 2008-08-21 Ashland-Südchemie-Kernfest GmbH Thermische Regenerierung von Gießereisand
DE102007045649B4 (de) 2007-09-25 2015-11-19 H2K Minerals Gmbh Verfahren zur Herstellung einer Form und/oder eines Kernes unter Verwendung von zerkleinerten natürlichen partikulären amorphen Kieselsäurematerialien im Gießereibereich und Binderzusammensetzung
US8221669B2 (en) * 2009-09-30 2012-07-17 Stratasys, Inc. Method for building three-dimensional models in extrusion-based digital manufacturing systems using ribbon filaments
DE102011105688A1 (de) 2011-06-22 2012-12-27 Hüttenes-Albertus Chemische Werke GmbH Verfahren zum schichtweisen Aufbau von Modellen
DK201170423A (en) 2011-08-02 2013-02-03 Bollerup Jensen As A low viscosity metal silicate composition
DE102011053205B4 (de) 2011-09-01 2017-05-24 Exone Gmbh Verfahren zum herstellen eines bauteils in ablagerungstechnik
DE102012020509A1 (de) * 2012-10-19 2014-06-12 Ask Chemicals Gmbh Formstoffmischungen auf der Basis anorganischer Bindemittel und Verfahren zur Herstellung von Formen und Kerne für den Metallguss
DE102012020510B4 (de) 2012-10-19 2019-02-14 Ask Chemicals Gmbh Formstoffmischungen auf der Basis anorganischer Bindemittel und Verfahren zur Herstellung von Formen und Kerne für den Metallguss
DE102012020511A1 (de) 2012-10-19 2014-04-24 Ask Chemicals Gmbh Formstoffmischungen auf der Basis anorganischer Bindemittel und Verfahren zur Herstellung von Formen und Kerne für den Metallguss
JP5986498B2 (ja) * 2012-12-19 2016-09-06 旭有機材株式会社 コーテッドサンドの製造方法及び鋳型の製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4233078A (en) * 1979-07-03 1980-11-11 Kaiser Aluminum & Chemical Corporation Refractory composition for forming a monolithic structure
US6139619A (en) * 1996-02-29 2000-10-31 Borden Chemical, Inc. Binders for cores and molds
US7807077B2 (en) * 2003-06-16 2010-10-05 Voxeljet Technology Gmbh Methods and systems for the manufacture of layered three-dimensional forms
US7381360B2 (en) * 2003-11-03 2008-06-03 Hewlett-Packard Development Company, L.P. Solid free-form fabrication of three-dimensional objects
US20100326620A1 (en) * 2007-10-30 2010-12-30 Ashland-Südchemie-Kernfest GmbH Mould material mixture having improved flowability

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11104029B2 (en) * 2016-02-26 2021-08-31 Hewlett-Packard Development Company, L.P. Three-dimensional (3D) printing
US10981215B2 (en) * 2017-06-30 2021-04-20 HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung Method for producing a moulding material mixture and a moulded body thereof in the casting industry and kit for use in this method
NL2020447B1 (en) * 2018-02-15 2019-08-22 Concr3De B V Additive manufacturing of an inorganic geopolymer object
WO2019160405A1 (en) 2018-02-15 2019-08-22 Concr3De B.V. Additive manufacturing of an inorganic geopolymer object
US11179768B2 (en) * 2018-05-28 2021-11-23 Abb Sp. Z O.O Method of preparation of sand casting moulds with a protective coating
FR3083472A1 (fr) * 2018-07-07 2020-01-10 Ecole Centrale De Nantes Procédé et dispositif de fabrication additive par agglomération d’un matériau granulaire
WO2020011734A1 (fr) 2018-07-07 2020-01-16 Ecole Centrale De Nantes Procédé et dispositif de fabrication additive par agglomération d'un matériau granulaire
US11992873B2 (en) 2018-07-07 2024-05-28 Ecole Centrale De Nantes Method and device for additive manufacturing by agglomeration of a granular material
CN114585460A (zh) * 2018-07-07 2022-06-03 南特中央理工大学 由粒状材料的聚结进行增材制造的方法和设备
RU2696590C1 (ru) * 2018-11-14 2019-08-06 Федеральное государственное бюджетное образовательное учреждение высшего образования "Чувашский государственный университет имени И.Н. Ульянова" Способ приготовления жидкостекольного связующего для получения формовочных и стержневых смесей
US11123789B2 (en) * 2019-01-22 2021-09-21 Lift Technology Method for inorganic binder castings
US20220016694A1 (en) * 2019-01-22 2022-01-20 Lift Technology Method for inorganic binder castings
US11759848B2 (en) * 2019-01-22 2023-09-19 Lift Technology Method for inorganic binder castings
FR3099999A1 (fr) * 2019-08-22 2021-02-26 Safran Helicopter Engines Procédé de fabrication additive d’un moule pour fonderie et procédé de fabrication d’une pièce métallique mettant en œuvre ledit procédé
CN111377744A (zh) * 2020-03-24 2020-07-07 共享智能铸造产业创新中心有限公司 3d打印陶瓷材料用硫酸盐基复合粘结剂

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