EP3986634A1 - Moules de fonderie poteyés pouvant être obtenus à partir d'un mélange de matières à mouler contenant un liant inorganique et des composés phosphatés et des composés d'oxyde de bore et procédé pour les fabriquer et leur utilisation - Google Patents

Moules de fonderie poteyés pouvant être obtenus à partir d'un mélange de matières à mouler contenant un liant inorganique et des composés phosphatés et des composés d'oxyde de bore et procédé pour les fabriquer et leur utilisation

Info

Publication number
EP3986634A1
EP3986634A1 EP20740224.9A EP20740224A EP3986634A1 EP 3986634 A1 EP3986634 A1 EP 3986634A1 EP 20740224 A EP20740224 A EP 20740224A EP 3986634 A1 EP3986634 A1 EP 3986634A1
Authority
EP
European Patent Office
Prior art keywords
weight
molds
molding material
water
cores
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
EP20740224.9A
Other languages
German (de)
English (en)
Inventor
Felix MÜCK
Tamara Jacqueline HOLTHAUSEN
Ronja Resch
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.)
ASK Chemicals GmbH
Original Assignee
ASK Chemicals GmbH
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 ASK Chemicals GmbH filed Critical ASK Chemicals GmbH
Publication of EP3986634A1 publication Critical patent/EP3986634A1/fr
Pending legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16—Compositions 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
    • B22C1/18—Compositions 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
    • B22C1/185—Compositions 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 containing phosphates, phosphoric acids or its derivatives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16—Compositions 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
    • B22C1/162—Compositions 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 use of a gaseous treating agent for hardening the binder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16—Compositions 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
    • B22C1/18—Compositions 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
    • B22C1/186—Compositions 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
    • B22C1/188—Alkali metal silicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C3/00—Selection of compositions for coating the surfaces of moulds, cores, or patterns
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C9/00—Moulds or cores; Moulding processes
    • B22C9/02—Sand moulds or like moulds for shaped castings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C9/00—Moulds or cores; Moulding processes
    • B22C9/10—Cores; Manufacture or installation of cores
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C9/00—Moulds or cores; Moulding processes
    • B22C9/12—Treating moulds or cores, e.g. drying, hardening
    • 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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/14—Shaped 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
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    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/4505—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements characterised by the method of application
    • C04B41/4535—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements characterised by the method of application applied as a solution, emulsion, dispersion or suspension
    • C04B41/4539—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements characterised by the method of application applied as a solution, emulsion, dispersion or suspension as a emulsion, dispersion or suspension
    • C—CHEMISTRY; METALLURGY
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    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
    • C04B41/5037—Clay, Kaolin
    • C—CHEMISTRY; METALLURGY
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3409—Boron oxide, borates, boric acids, or oxide forming salts thereof, e.g. borax
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3427—Silicates other than clay, e.g. water glass
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/447—Phosphates or phosphites, e.g. orthophosphate, hypophosphite
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5409—Particle size related information expressed by specific surface values
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
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    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5436—Particle 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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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5445—Particle size related information expressed by the size of the particles or aggregates thereof submicron sized, i.e. from 0,1 to 1 micron
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9669—Resistance against chemicals, e.g. against molten glass or molten salts
    • C04B2235/9676—Resistance against chemicals, e.g. against molten glass or molten salts against molten metals such as steel or aluminium

Definitions

  • the invention relates to sized casting molds for metal casting obtainable from molding material mixtures based on inorganic binders, containing at least one phosphate-containing compound and at least one oxidic boron compound, namely sized, water-glass-bound molds and cores comprising at least one refractory basic molding material, water glass as an inorganic binder and amorphous particulate Silicon dioxide, as well as one or more oxidic boron compounds and one or more phosphate-containing compounds, in particular for the production of castings from iron alloys. Furthermore, the invention relates to a method for the production of sized foundry moldings and their use, in particular for the production of castings from iron alloys.
  • the size is a water-based size.
  • Casting molds are essentially composed of cores and molds that represent the negative molds of the casting to be produced.
  • the casting mold (including the plural) is used as a synonym for cores, forms (each individually) and for cores and forms (together).
  • Cores and molds are based on a refractory material, for example quartz sand, and a suitable binding agent, which gives the casting mold sufficient mechanical strength after it has been removed from the mold.
  • a refractory basic molding material is used, which is coated with a suitable binding agent.
  • the refractory basic molding material is preferably in a free-flowing form so that it can be filled into a suitable hollow mold and compacted there.
  • the binding agent creates a firm bond between the particles of the basic mold material so that the casting mold has the required mechanical stability.
  • Casting molds have to meet various requirements. During the casting process itself, they must first have sufficient strength and temperature resistance in order to be able to absorb the liquid metal in the cavity formed from one or more casting molds. After the start of the solidification process, the mechanical stability of the casting is ensured by a solidified metal layer that forms along the walls of the casting mold. The material of the casting mold must now decompose under the influence of the heat given off by the metal in such a way that it loses its mechanical strength, i.e. the cohesion of the individual particles of the refractory material is broken. Ideally, the mold disintegrates again into fine sand that can be easily removed from the casting.
  • the surfaces of the foundry mold body are coated with a finishing layer, especially those surfaces that come into contact with the cast metal. Finishes form a boundary or barrier layer between the form / core and metal, including for the targeted suppression of failure mechanisms at these points or for the use of metallurgical effects.
  • coatings in foundry technology should primarily fulfill the following functions:
  • the surface of the casting must be reworked in a complex manner in order to achieve the desired surface properties. This requires additional work steps and thus a decrease in productivity and an increase in costs. If the defects occur on surfaces of the casting that are poorly or not at all accessible, this can also lead to a loss of the casting.
  • the size can have a metallurgical influence on the casting, for example by selectively transferring additives into the casting on the surface of the casting, which additions improve the surface properties of the casting.
  • the coatings form a layer which chemically isolates the casting mold from the liquid metal. This reduces the adhesion between the casting and the casting mold, so that the casting can be removed from the casting mold without difficulty.
  • the size can also be used to control the heat transfer between the liquid metal and the casting mold in a targeted manner, for example to bring about the formation of a certain metal structure through the cooling rate.
  • a size usually consists of an inorganic refractory substance and a binder, the sizes being dissolved or slurried in a suitable carrier liquid, for example water or alcohol. If possible, one would like to forego the use of alcohol-containing coatings and instead use aqueous systems, since the organic solvents cause emissions in the course of the drying process.
  • a suitable carrier liquid for example water or alcohol.
  • inorganic binder systems have been developed or further developed in recent years, the use of which means that emissions of CO 2 and hydrocarbons in the production of metal molds can be avoided or at least significantly minimized.
  • inorganic binder systems is often associated with other disadvantages, which are described in detail in the following explanations.
  • inorganic binders Compared to organic binders, inorganic binders have the disadvantage that the casting molds made from them have relatively low strengths. This is particularly evident immediately after the casting mold has been removed from the tool. However, good strengths at this point are particularly important for the production of complex and / or thin-walled molded parts and for safe handling. Molds and cores produced with inorganic binders such as water glass also have a comparatively low resistance to atmospheric moisture or to water or aqueous moisture. This means that it is often not possible to apply a water-based or water-containing size or to store such foundry molds or cores for a longer period of time, as is customary with organic molding material binders.
  • Inorganic binder systems have the disadvantage compared to organic binder systems that the seeding behavior, i.e. the ability of the casting mold to quickly degenerate into a light, pourable form after metal casting (under mechanical stress) is often worse in the case of purely inorganically manufactured casting molds (e.g. those that use water glasses as a binder) than for casting molds made with an organic binder . This is especially true for cast iron applications.
  • EP 1802409 B1 discloses that higher instant strengths and higher resistance to atmospheric moisture can be achieved through the use of a fireproof molding base material, a binder based on water glass and the addition of particulate amorphous silicon dioxide.
  • DE 102013106276 A1 discloses that a higher resistance to humidity and to water-based sizes can be achieved by using a lithium-containing molding material mixture based on an inorganic binder, in particular in combination with amorphous silicon dioxide. This ensures safe handling of even complicated casting molds.
  • EP 2097192 B1 discloses that by using one or more phosphorus-containing compounds in combination with amorphous silicon dioxide, a significantly higher heat resistance can be achieved.
  • test specimens produced from phosphate-containing molding material mixtures show significantly improved thermal stability with a time delay or reduction in “hot deformation”. It is also disclosed that, despite the high strengths, casting molds produced from the molding material mixtures according to the invention, in particular in the case of aluminum casting, show very good disintegration.
  • WO 2015058737 A 2 discloses that higher flexural strengths can be achieved after storage in atmospheric humidity by using one or more boron oxide compounds. This addition ensures improved handling of even complicated casting molds. Furthermore, it is disclosed that, despite the high strength of the casting molds produced from the molding material mixtures, they show very good disintegration, in particular in the case of aluminum casting.
  • inorganic molding material binders in particular water-containing molding material binders, should also gain in importance in the production of molds and cores in the future in the field of steel and iron casting.
  • organic carrier liquids as far as possible or, preferably, water-based sizes, i.e. Sizing with water as the sole carrier liquid or as at least a predominant proportion (in terms of weight) of the carrier liquid.
  • foundry moldings in particular molds and cores made with inorganic molding material binders, in particular with water-containing molding material binders, have a low stability to the action of water or aqueous moisture.
  • the water contained in water-based sizing compositions can consequently damage the inorganically bound forms and cores treated (sized) with it. In particular, this can disadvantageously reduce the strength of the shapes and cores that have been finished in this way.
  • the invention was therefore based on the object of providing an inorganic molding material mixture for the production of casting molds for metal processing, in particular of iron and iron alloys, which is particularly effective in improving the stability towards environmentally friendly water-based coatings and at the same time has a high level of strength in the coating-drying Process guarantees that is necessary in the automated manufacturing process for the production of particularly thin-walled or filigree or complex, smooth casting molds.
  • the casting mold should have high storage stability and very good disintegration properties.
  • inorganic molding material mixtures used according to the invention can also be used to produce complex component geometries with reduced emissions or emission-free in cast iron.
  • the casting molds according to the invention namely molds or cores, for metal processing are obtainable from at least one molding material mixture
  • binding agent comprising at least water glass
  • phosphate-containing compound in particular in powder form or dissolved, e.g. dissolved in water
  • Part of the binder are the water glass, the particulate amorphous silicon dioxide, the oxidic boron compound and the phosphate-containing compound.
  • Customary and known materials can be used as the refractory base molding material for the production of casting molds.
  • quartz sand, zirconium sand or chrome ore sand, olivine, vermiculite, bauxite, chamotte, and artificial mold base materials are suitable. It is not necessary to only use new sand. In order to conserve resources and avoid landfill costs, it is even advantageous to use as high a proportion as possible of regenerated used sand, as can be obtained from used molds by recycling.
  • a refractory base molding material is understood to mean substances that have a high melting point (melting temperature).
  • the melting point of the refractory base molding material is preferably greater than 600 ° C., preferably greater than 900 ° C., particularly preferably greater than 1200 ° C. and particularly preferably greater than 1500 ° C.
  • the refractory basic molding material preferably makes up more than 80% by weight, in particular more than 90% by weight, particularly preferably more than 95% by weight, of the molding material mixture.
  • the regrind can make up at least about 70% by weight of the refractory base molding material, preferably at least about 80% by weight and particularly preferably greater than 90% by weight.
  • the mean diameter of the refractory base molding materials is generally between 120 mm and 600 mm and preferably between 150 mm and 500 mm.
  • the particle size can be z. B. determined by sieving according to DIN ISO 3310. Particle geometries with the greatest length expansion to the smallest length expansion (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, e.g. are not fibrous.
  • the refractory basic molding material has a free-flowing state, in particular in order to be able to process the molding material mixture according to the invention in conventional core shooting machines.
  • the water glasses contain dissolved alkali silicates and can be produced by dissolving vitreous lithium, sodium and / or potassium silicates in water.
  • the water glass preferably has a molar module SiO 2 / M 2 O (cumulative with different M's, ie in total) in the range from 1.6 to 4.0, in particular 2.0 to less than 3.5, where M is Lithium, sodium and / or potassium.
  • the binders can also be based on water glasses that contain more than one of the alkali ions mentioned, such as. B.
  • Particularly preferred is a water glass which has a proportion of lithium ions, in particular amorphous lithium silicates, lithium oxides and lithium hydroxides, or a ratio as described in DE 102013106276 A1.
  • the water glasses have a solids content in the range from 25 to 65% by weight, preferably from 33 to 55% by weight, in particular from 30 to 50% by weight.
  • the solids content relates to the amount of SiO 2 and M 2 O contained in the water glass.
  • the waterglass-based binder preferably between 0.5% by weight and 5% by weight of the waterglass-based binder is used, preferably between 0.75% by weight and 4% by weight, particularly preferably between 1% by weight. -% and 3.5% by weight, each based on the basic molding material.
  • powdery or particulate is understood to mean a solid powder (including dusts) or granules that are pourable and thus screenable.
  • the molding mixture according to the invention contains a portion of a particulate amorphous silicon dioxide in order to increase the strength level of the casting molds produced with such molding mixtures.
  • An increase in the strength of the casting mold, in particular an increase in the heat strength, can be advantageous in the automated production process.
  • Synthetically produced amorphous silica is particularly preferred.
  • 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 dust). Both synthetically produced and naturally occurring silicas can be used as amorphous SiO 2 .
  • the latter are z. B. from DE 102007045649, but are not preferred, since they usually contain not inconsiderable crystalline components and are therefore classified as carcinogenic.
  • Understood by synthetically and not naturally occurring amorphous SiO 2 ie the synthetic production comprises a deliberately carried out chemical reaction, as it is initiated by a person, e.g. B.
  • silica sols by ion exchange processes as alkali silicate solutions, the distribution from alkali metal silicate solutions, the flame hydrolysis of silicon tetrachloride, the reaction of quartz sand with coke in the electric arc furnace in the production of ferrosilicate and silicon.
  • the amorphous SiO 2 produced by the two last-mentioned processes is also referred to as pyrogenic SiO 2 .
  • synthetic amorphous silicon dioxide is understood to mean only precipitated silica (CAS No. 112926-00-8) and SiO 2 produced by flame hydrolysis (Pyrogenic Slica, Fumed Silica, CAS No. 112945-52-5), while that in the product resulting from the manufacture of ferrosilicon or silicide is referred to merely as amorphous silicon dioxide (silica fume, microsilica, CAS No. 69012-64-12).
  • the product resulting from femosilicon or silicon production is also understood to be amorphous SiO 2 .
  • Amorphous silicon dioxide produced by thermal decomposition of ZrSi04 (described in DE 102012020509 A1) and SiO 2 produced by oxidation of metallic Si by means of an oxygen-containing gas (described in DE 102012020510 A1) are particularly preferred.
  • Quartz glass powder is also preferred (mainly amorphous silicon dioxide), which was produced from crystalline quartz by melting and rapid cooling again, so that the particles are spherical and not splintery (described in DE 102012020511 A1).
  • the mean particle size of the amorphous silicon dioxide is preferably less than 100 mm, in particular less than 70 mm.
  • the sieve residue of the particulate amorphous SiO 2 when passing through a sieve with 125 mm mesh size (120 mesh) is preferably not more than 10% by weight, particularly preferably not more than 5% by weight and very particularly preferably not more than 2 Wt%. Irrespective of this, the sieve residue on a sieve with a mesh size of 63 ml is less than 10% by weight, preferably less than 8% by weight.
  • This sieving residue is determined using the machine sieving method described in DIN 66165 (Part 2), a chain ring being used as a sieving aid.
  • the mean primary particle size of the particulate amorphous silicon dioxide can be between 0.05 mm and 10 mm, in particular between 0.1 mm and 5 mm and preferably between 0.1 mm and 2 mm.
  • the primary particle size can e.g. can be determined with the help of dynamic light scattering (e.g. Horiba LA 959) and checked by scanning electron microscope images (SEM images with e.g. Nova NanoSEM 230 from FEI). Furthermore, with the aid of the SEM images, details of the primary particle shape down to the order of 0.01 mm could be made visible.
  • the silicon dioxide samples were dispersed in distilled water and then placed on an aluminum holder covered with copper tape before the water was evaporated.
  • the specific surface area of the particulate amorphous silicon dioxide was determined with the aid of gas adsorption measurements (BET method) according to DIN 66131.
  • the specific surface of the particulate amorphous SiO 2 is between 1 and 200 m 2 / g, in particular between 1 and 50 nWg, particularly preferably between 1 and 19 m 2 / g. Possibly. the products can also be mixed, for example in order to obtain mixtures with specific particle size distributions in a targeted manner.
  • the purity of the amorphous SiO 2 can vary greatly depending on the production method and producer. Types having a silicon dioxide content of at least 85% by weight, preferably at least 90% by weight and particularly preferably at least 95% by weight, have proven to be suitable.
  • 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, each based on the basic molding material.
  • the ratio of water glass binder to particulate amorphous silicon dioxide can be varied within wide limits. This offers the advantage of greatly improving the initial strength of the molds and / or cores, ie the strength immediately after removal from the tool, without significantly affecting the final strength.
  • the final strengths should not be too high to avoid difficulties with the core disintegrating after casting to avoid, ie the basic mold material should be able to be easily removed from cavities of the casting mold after casting.
  • the amorphous SiO 2 is preferably contained in a proportion of 1 to 80% by weight, preferably 2 to 60% by weight, particularly preferably from 3 to 55% by weight. % and particularly preferably between 4 to 50% by weight. Or regardless of this, based on the ratio of solids content of the water glass (based on the oxides, ie total mass of alkali metal oxide and silicon dioxide) to amorphous SiO 2 of 10: 1 to 1: 1.2 (parts by weight) preferred.
  • the amorphous SiO 2 is preferably added to the refractory material before the addition of waterglass.
  • the solid mixture according to the invention contains one or more oxidic boron compounds, in particular in particulate form in powder form.
  • the mean particle size of the oxidic boron compound is preferably less than 1 mm, more preferably less than 0.5 mm, particularly preferably less than 0.25 mm.
  • the particle size of the oxidic boron compound is preferably greater than 0.1 mm, preferably greater than 1 ⁇ m and particularly preferably greater than 5 mm.
  • the residue on a sieve with a mesh size of 1.00 mm is less than 5% by weight, particularly preferably less than 2.0% by weight and particularly preferably less than 1.0% by weight.
  • the sieve residue on a sieve with a mesh size of 0.5 mm is preferably less than 20% by weight, preferably less than 15% by weight, particularly preferably less than 10% by weight and in particular preferably less than 5% by weight.
  • the sieve residue is preferably less than 50% by weight, more preferably less than 25% by weight and particularly preferably less than 15% by weight.
  • the sieve residue is determined using the machine sieving method described in DIN 66165 (Part 2), a chain ring being used as a sieving aid.
  • Oxidic boron compounds are understood to mean compounds in which the boron is in the +3 oxidation state. Furthermore, the boron is coordinated with oxygen atoms (in the first coordination sphere, i.e. as the closest neighbors) - either by 3 or 4 of oxygen atoms.
  • the oxidic boron compound is preferably selected from the group of borates, boric acids, boric anhydrides, borosilicates, borophosphates, borophosphosilicates and mixtures thereof, the oxidic boron compound preferably not containing any organic groups.
  • Boric acids are understood to mean orthoboric acid (empirical formula H3BO3) and meta or polyboric acids (empirical formula (HBQz) n).
  • Orthoboric acid occurs, for example, in water vapor sources and as the mineral sassolin.
  • Orthoboric acid can also be produced from borates (e.g. borax) by acid hydrolysis.
  • Meta- or polyboric acids can be produced, for example, from orthoboric acid by intermolecular condensation by heating.
  • Boric anhydride empirical formula B 2 O 3
  • Boric anhydride can be produced by annealing boric acids. Boric anhydride is obtained as a mostly vitreous, hygroscopic mass, which can then be turned into small pieces.
  • Borates are principally derived from boric acids. They can be of both natural and synthetic origin. Borates are composed of borate structural units in which the boron atom is surrounded by either 3 or 4 oxygen atoms as the closest neighbors. The individual structural units are mostly anionic and can either be isolated within a substance, e.g. in the case of orthoborate or with one another be linked, such as metaborate of
  • Units can be linked to form rings or chains - if one considers such a linked structure with corresponding B-O-B bonds, then it is anionic in the overall view.
  • borates which contain linked B-O-B units.
  • Orthorates are suitable, but not preferred.
  • Alkali and / or alkaline earth cations for example, but also, for example, zinc cations, in particular sodium or calcium cations, particularly preferably calcium, serve as counterions to the anionic borate units.
  • the molar molar ratio between cation and boron can be described in the following way: where M stands for the cation and x for divalent cations 1 and for monovalent cations 2.
  • the lower limit is preferably greater than 1:20, preferably greater than 1:10 and particularly preferably greater than 1: 5.
  • borates in which trivalent cations serve as counterions to the anionic borate units for example aluminum cations in the case of aluminum borates.
  • Natural borates are mostly hydrated, ie water is contained as structural water (as OH groups) and / or as crystal water (H 2 O molecules).
  • borax or borax decahydrate (disodium tetraborate decahydrate) can be considered, whose molecular formula in the literature is either
  • Both hydrated and non-hydrated borates can be used, but the hydrated borates are preferably used.
  • amorphous and crystalline borates can be used.
  • Alkali or alkaline earth borate glasses are understood as amorphous borates, for example.
  • Borosilicates, bonophosphates and borophosphosilicates are understood to mean compounds which are mostly amorphous / glass-like.
  • these compounds there are not only neutral and / or anionic boron-oxygen coordinations (for example neutral BO 3 units and anionic BCV units), but also neutral and / or anionic silicon-oxygen and / or Phos - phosphorus-oxygen coordination - the silicon is in the +4 oxidation state and the phosphorus is in the +5 oxidation state.
  • the coordinations can be linked to one another via bridging oxygen atoms, such as Si-OB or P-OB.
  • borosilicates borophosphates and borophosphosilicates
  • metal oxides in particular alkali and earth metal oxides, which serve as so-called network modifiers, can be incorporated.
  • the proportion of boron (calculated as B 2 O 3 ) in the borosilicates, borophosphates and borophosphosilicates is preferably greater than 15% by weight, preferably greater than 30% by weight, particularly preferably greater than 40% by weight, based on the total mass of the corresponding borosilicate, bonophosphate or borophosphosilicate.
  • boric acids from the group of borates, boric acids, boric anhydrides, borosilicates, borophosphates and / or borophosphosilicates, however, the borates, borophosphates and borophosphosilicates and in particular the alkali and alkaline earth borates are clearly preferred.
  • One reason for this selection is the strong hygroscopicity of boric anhydride, which impairs its possible use as a powder additive in the event of prolonged storage. Casting tests with an aluminum melt have also shown that borates lead to significantly better cast surfaces than boric acids, which is why the latter are less preferred.
  • Borates are particularly preferably used. Particular preference is given to using alkali and / or terminal alkali borates, of which sodium borates and / or calcium borates are preferred. Calcium borate is particularly preferred.
  • the proportion of the oxidic boron compound, based in each case on the refractory base molding material, is preferably less than 1.0% by weight, preferably less than 0.4% by weight, particularly preferably less than 0.2% by weight and particularly preferred less than 0.1% by weight.
  • the lower limit is preferably greater than 0.002% by weight, preferably greater than 0.005% by weight, particularly preferably greater than 0.01% by weight and particularly preferably greater than 0.02% by weight.
  • the molding material mixture used according to the invention also contains a phosphate-containing compound.
  • a phosphate-containing compound are inorganic phosphate compounds in which the phosphorus is in the +5 oxidation state and is surrounded by oxygen atoms in the immediate vicinity.
  • the phosphate can be in the form of an alkali metal phosphate or an alkaline earth metal phosphate, with alkali metal phosphates and in particular the sodium salts being preferred.
  • Both orthophosphates and also polyphosphates, pyrophosphates or metaphosphates can be used as phosphates, polyphosphates and metaphosphates being preferred, sodium polyphosphates and sodium metaphosphates being very particularly preferred.
  • the phosphates can be produced, for example, by neutralizing the corresponding acids with a corresponding base, for example an alkali metal base such as NaOH, or possibly also an alkaline earth metal base, although not all of the negative charges on the phosphate necessarily have to be replaced by metal ions.
  • the phosphates can be introduced into the molding material mixture either in crystalline or in amorphous form.
  • Polyphosphates are understood to mean, in particular, linear phosphates which comprise more than one phosphorus atom, the phosphorus atoms being connected to one another via oxygen bridges.
  • Polyphosphates are obtained by condensation of orthophosphate ions with elimination of water, so that a linear chain of PO4 tetrahedra is obtained, each of which is connected by corners.
  • a polyphosphate can comprise up to several hundred PO 4 tetrahedra. However, preference is given to using polyphosphates with shorter chain lengths.
  • N preferably has values from 3 to 100, particularly preferably 5 to 50. It is also possible to use more highly condensed polyphosphates, ie polyphosphates in which the PO 4 tetrahedra are connected to one another via more than two corners and therefore exhibit polymerization in two or three dimensions.
  • Metaphosphate is understood to mean cyclic structures that are built up from PO4 tetrahedra that are each connected to one another via corners. Metaphosphates have the general formula where n is at least 3. Preferably, n has values from 3 to 10.
  • Both individual phosphates and mixtures of different phosphates can be used as the phosphate-containing compound.
  • the phosphate-containing compound independently preferably contains between 40% by weight and 90% by weight, particularly preferably between 50% and 80% by weight phosphorus, that is to say calculated on P2O5.
  • the phosphate-containing compound can itself be added to the molding material mixture in solid or dissolved form.
  • the phosphate-containing compound is preferably added to the molding material mixture as a solid.
  • the weight ratio of the oxidic boron compound to the phosphate-containing compound can vary over wide ranges and is preferably from 1:30 to 1: 1, preferably from 1:25 to 1: 2, particularly preferably from 1:20 to 1: 3.
  • the stoichiometric ratio of P: B is considered. If the stoichiometric ratio of P: B is £ 1, the compound is assigned to the phosphate-containing compounds, all other compounds are counted as an oxidic boron compound Surprisingly, it has also been shown that the moisture resistance of the sized molds and / or cores is improved by adding combinations according to the invention of oxidic boron compounds and phosphate-containing compounds to the molding material mixture, and thus their strength and storage stability are increased.
  • the molding material mixture according to the invention contains a proportion of platelet-shaped lubricants, in particular graphite or MoS2.
  • the amount of flake-form lubricant added, in particular graphite is preferably 0.05% by weight to 1% by weight, particularly preferably 0.05% by weight to 0.5% by weight, based on the basic molding material.
  • surface-active substances in particular surfactants
  • Anionic surfactants are preferably used for the molding material mixture according to the invention.
  • surfactants with sulfuric acid or sulfonic acid groups or their salts may be mentioned here.
  • the pure surface-active substance, in particular the surfactant, based on the weight of the refractory base molding material is preferably in a proportion of 0.001% by weight to 1% by weight, particularly preferably 0.01% by weight to 0, 2% by weight.
  • the molding material mixture according to the invention represents an intensive mixture of at least the mentioned constituents.
  • the particles of the refractory molding base material are preferably coated with a layer of the binder.
  • a layer of the binder By evaporating the water present in the binding agent (e.g. approx. 40-70% by weight, based on the weight of the binding agent), firm cohesion between the particles of the refractory basic molding material can then be achieved.
  • the casting molds produced with the molding material mixture according to the invention surprisingly show very good disintegration even after casting, even with iron and steel casting, so that the casting mold can easily be removed from narrow and angled sections of the casting after casting leaves.
  • the casting molds are generally suitable for casting metals such as light metals, non-ferrous metals or ferrous metals.
  • the molding material mixture according to the invention is particularly preferably suitable for the casting of iron and iron alloys.
  • the invention further relates to a method for producing sized casting molds for metal processing, the molding material mixture mentioned above being used.
  • the method according to the invention comprises the steps:
  • the procedure is generally such that first the refractory molding base material is initially introduced and then the binder and the additive are added with stirring.
  • the additives described above can be added to the molding material mixture in any form. They can be dosed individually or as a mixture.
  • the binder is provided as a two-component n-system, a first liquid component containing the water glass and optionally a surfactant (see above), and a second, but solid component containing the particulate silicon dioxide and one or more oxidic ones Boron compounds and one or more phosphate-containing compounds and possibly other old solid additives mentioned above, with the exception of the basic molding materials.
  • the refractory basic molding material is preferably placed in a mixer and then preferably the solid component (s) of the binder are first added and mixed with the refractory basic molding material.
  • the mixing time is chosen so that the refractory molding base material and solid binder component are thoroughly mixed.
  • the mixing time depends on the amount of molding material mixture to be produced and on the mixing unit used.
  • the mixing time is preferably between 1 and 5 minutes.
  • the liquid component of the binding agent is then added, preferably with further agitation of the mixture, and the mixture is then preferably further mixed until a uniform layer of the binding agent has formed on the grains of the refractory molding base material.
  • the mixing time depends on the amount of molding material mixture to be produced and on the mixing unit used.
  • the duration for the mixing process is preferably selected from 1 to 5 minutes.
  • a liquid component is understood to mean both a mixture of various liquid components and the entirety of all liquid individual components, the latter being able to be added to the molding material mixture together or one after the other.
  • a solid component is also understood to mean both the mixture of individual or all of the solid components described above and the entirety of all solid individual components, the latter being able to be added to the molding material mixture together or one after the other.
  • the liquid component of the binder can also first be added to the refractory base molding material and only then the solid component can be added to the mixture.
  • 0.05% by weight to 0.3% by weight of water based on the weight of the molding material, is added to the refractory base molding material and only then are the solid and liquid components of the binder added.
  • the mold material mixture is then brought into the desired shape.
  • the mold material mixture can be shot into the mold by means of a core shooter with the help of compressed air.
  • the molding material mixture is then cured, whereby all methods can be used which are known for binders based on water glass, eg hot curing, gassing with CO 2 or air or a combination of both and curing by liquid or solid catalysts. Heat curing is preferred.
  • water is removed from the molding material mixture. This presumably also initiates condensation reactions between silanol groups, so that crosslinking of the water glass occurs.
  • the heating can take place, for example, in a mold which preferably has a temperature of 100.degree. C. to 300.degree. C., particularly preferably a temperature of 120.degree. C. to 250.degree. It is possible to cure the casting mold completely in the molding tool. However, it is also possible to cure the casting mold only in its edge area, so that it has sufficient strength to be able to be removed from the molding tool.
  • the casting mold can then be completely cured by removing other water from it. This can be done in an oven, for example.
  • the water can also be removed, for example, by evaporating the water under reduced pressure.
  • the hardening of the casting mold can be accelerated by blowing heated air into the mold.
  • the water contained in the binding agent is quickly transported away, so that the casting mold is solidified in periods of time suitable for industrial use.
  • the temperature of the air blown in is preferably 100.degree. C. to 180.degree. C., particularly preferably 120.degree. C. to 150.degree.
  • the flow rate of the heated air is preferably adjusted in such a way that the casting mold is cured in periods of time suitable for industrial use.
  • the time periods depend on the size of the molds made. The aim is to cure in less than 5 minutes, preferably less than 2 minutes. However, longer periods of time may also be required for very large molds.
  • the removal of water from the molding material mixture can also take place in such a way that the heating of the molding material mixture is brought about or supported by irradiating microwaves. It would be conceivable, for example, to mix the basic molding material with the solid, powdery component (s), to apply this mixture in layers to a surface and to print the individual layers with the help of a liquid binder component, in particular with the help of a water glass, the layer-by-layer application the solid mixture is followed by a printing process with the aid of the liquid binder
  • the entire mixture can be heated in a microwave oven.
  • the at least partially cured cores and molds produced in this way are then provided, at least on partial areas, with the size composition according to the invention in the form of a coating or a coating.
  • the sizing composition can be brought into contact with the core or the mold by spraying, brushing, dipping or flooding.
  • the sizing composition is a liquid in use, with solids suspended in it.
  • the carrier liquid is the constituent that can be evaporated at 160 ° C. and normal pressure (1013 mbar) and, in this sense, by definition, that which is not solid.
  • the carrier liquid can be partially or completely formed by water.
  • the carrier liquid contains more than 50% by weight, preferably 75% by weight, in particular more than 80% by weight, possibly more than 95% by weight, of water.
  • the other components in the carrier liquid can be organic solvents. Suitable solvents are alcohols, including polyalcohols and polyether alcohols. Exemplary alcohols are ethanol, n-propanol, isopropanol, n-butanol, glycols, glycol monoethers and glycol monoesters.
  • the solids content of the ready-to-use size composition is preferably set in the range from 10 to 60% by weight, or in the sales form (before dilution, in particular with water), in particular 30 to 80% by weight.
  • the size composition comprises at least 20% by weight of carrier liquid, preferably greater than 40% by weight.
  • the sizing composition comprises at least one refractory base material in powder form before being added to the sizing composition.
  • the refractory base material is used to close the pores in a casting mold against the penetration of the liquid metal.
  • the refractory base material also provides thermal insulation between the casting mold and the liquid metal.
  • Particularly suitable refractory base materials are materials which have a melting point which is at least 200 ° C. above the temperature of the liquid metal to be cast (at least greater than 900 ° C.) and independently of this does not react with the metal as much as possible.
  • Pyrophyllite, mica, zirconium silicate, andalusite, chamotte, iron oxide, kyanite, bauxite, olivine, aluminum oxide, quartz, talc, calcined kaolins (metakaolin) and / or graphite alone or as mixtures thereof can be used as refractory raw materials (for the size) .
  • the passage portion D10 can preferably be from 0.01 mm to 5 mm, more preferably from 0.01 mm to 1 mm, particularly preferably from 0.01 mm to 0.2 mm for the grain size.
  • the clay can preferably have a passage fraction D01 of 0.001 mm to 0.2 mm, more preferably from 0.001 mm to 0.1 mm, particularly preferably from 0.001 mm to 0.05 mm for the particle size.
  • the passage portion D90 is preferably from 100 mm to 300 mm, more preferably from 150 mm to 250 mm, particularly preferably from 200 mm to 250 mm.
  • the passage portion D50 of the mica can preferably be from 45 mm to 125 mm, more preferably from 63 mm to 125 mm, particularly preferably from 75 mm to 125 mm.
  • the passage portion D10 can preferably have a grain size from 1 mm to 63 mm, more preferably from 5 mm to 45 mm, particularly preferably from 10 mm to 45 mm.
  • the passage portion D01 can preferably be from 0.1 mm to 10 mm, more preferably from 0.5 mm to 10 mm, particularly preferably from 1 mm to 5 mm.
  • the particle diameter of the refractory base materials of the size is not particularly restricted; any customary grain sizes from 1 mm to 300 mm, particularly preferably from 1 mm to 280 mm, can be used.
  • the grain size distribution of the individual solid constituents of the size composition can be determined using the passage proportions D90, D50, D10 and D01. These are a measure of the particle size distribution.
  • the passage proportions D90, D50, D10 or D01 denote the proportions in 90%,
  • the grain size and the passage proportions D90, D50, D10 and D01 can be determined using laser diffraction granulometry in accordance with ISO 13320. The percentage of passage is given on a volume basis. In the case of non-spherical particles, a hypothetical spherical grain size is calculated and the corresponding diameter is used as a basis. The grain size is therefore to be equated with the calculated diameter.
  • the particle diameter and its distribution is determined by laser diffraction in a water / isopropanol mixture, the suspension being obtained (only) by stirring, with a Horiba LA-960 laser light scattering spectrometer from Retsch based on static light scattering (according to DIN / ISO 13320) and by evaluation using the Fraunhofer model.
  • the grain size is selected so that a stable structure is created in the coating and that the size composition e.g. can easily be distributed on the wall of the mold with a spray device.
  • the size composition according to the invention can comprise at least one adjusting agent.
  • the adjusting agent causes an increase in the viscosity of the size, so that the solid constituents of the size composition do not sink in the suspension or only sink to a small extent. Both organic and inorganic materials or mixtures of these materials can be used to increase the viscosity.
  • Swellable sheet silicates which are capable of storing water between the layers, can be contained as adjusting agents;
  • the swellable sheet silicate can preferably be selected from attapulgite (palygorskite), serpentines, kaolins, smectites (such as saponite, montmorillonite, beidellite and nontronite), vermiculite, IIIite, spiolite, synthetic lithium-magnesium sheet silicate, Laponite RD and mixtures thereof
  • Attapulgite (palygorskite), serpentines, smectites (such as saponite, beidellite and nontronite), vermiculite, lllite, spiolite, synthetic lithium-magnesium phyllosilicate, Laponite RD and mixtures thereof are preferred; the swellable phyllosilicate can particularly preferably be attapulgite.
  • organic thickeners can also be selected as thickening agents, since these can be dried to such an extent after the protective coating has been applied that they hardly give off any water when they come into contact with the liquid metal.
  • swellable polymers such as carboxymethyl, methyl, ethyl, hydroxyethyl and hydroxypropyl cellulose, plant mucilages, polyvinyl alcohols, polyvinyl pyrrolidone, pectin, gelatin, agar agar, polypeptides and / or alginates can be used as organic setting materials.
  • the proportion of inorganic adjusting agents, based on the total size composition is preferably selected to be 0.1 to 5% by weight, preferably 0.5 to 3% by weight, particularly preferably 1 to 2% by weight.
  • the proportion of organic adjusting agents, based on the total size composition is preferably 0.01 to 1% by weight, preferably 0.01 to 0.5% by weight, particularly preferably 0.01 to 0.1% by weight. % chosen.
  • the size composition can e.g. the combination of certain clays as ingredients of the sizes, which also function as adjusting agents.
  • a combination of is particularly suitable as clay materials
  • the size (especially as a concentrate) contains
  • (A3) 1 to 20 parts by weight of sodium bentonite, based on the ratio of components (A1), (A2) and (A3) relative to one another, and
  • the total clay content of the above clays in the size composition is 0.1 to 4.0% by weight, preferably 0.5 to 3.0% by weight and particularly preferably 1.0 to 2.0% by weight, based on the solids content of the size composition.
  • the size composition comprises at least one binder as a further component.
  • the binder enables better fixation of the size composition or the protective coating produced from the size composition on the surface of the casting mold.
  • the binding agent increases the mechanical stability of the size coating, so that less erosion is observed under the action of the liquid metal.
  • the binder preferably hardens irreversibly, so that an abrasion-resistant coating is obtained. Particularly preferred are binders that do not re-soften on contact with atmospheric moisture.
  • Clays for example, especially bentonite and / or kaolin, can be used as binders.
  • binders are, for example, starch, dextrin, peptides, polyvinyl alcohol, polyvinyl acetate copolymers, polyacrylic acid, polystyrene, polyvinyl acetate-polyacrylate dispersions and mixtures thereof.
  • the proportion of the binder is preferably in the range from 0.1 to 20% by weight, particularly preferably 0.5 to 5% by weight and particularly preferably 0.2 to 2% by weight, based on the solids content of the size composition, elected.
  • the size composition contains a proportion of graphite.
  • the proportion of graphite is preferably selected in the range from 0 to 30% by weight, preferably 1 to 25% by weight, and particularly preferably from 1 to 20% by weight, based on the solids content of the size composition. In iron casting, graphite has a beneficial effect on the surface quality of the casting.
  • Anionic and non-anionic surfactants in particular those with an HLB value of at least 7, can be used as wetting agents for the size.
  • An example of such a wetting agent is disodium dioctyl sulfosucinate.
  • the wetting agent is preferably used in an amount of 0.01 to 1% by weight, preferably 0.05 to 0.3% by weight, based on the ready-to-use size composition.
  • Defoamers also called antifoam agents, can be used to prevent foam formation during the production of the sizing composition or when the same is applied. Foam formation when the sizing composition is applied can lead to an uneven layer thickness and holes in the coating. Silicone or mineral oil, for example, can be used as defoamers.
  • the defoamer is preferably present in an amount from 0.01 to 1% by weight, preferably from 0.05 to 0.3% by weight, based on the ready-to-use size composition.
  • Customary pigments and dyes can optionally be used in the size composition. These are added to provide a different contrast, e.g. between different layers, or to bring about a stronger separation effect of the coating from the casting.
  • pigments are red and yellow iron oxide and graphite.
  • dyes are commercially available dyes such as the Luconyl® color range from BASF SE.
  • the dyes and pigments are preferably present in an amount from 0.01 to 10% by weight, preferably from 0.1 to 5% by weight, based on the solids content of the size composition.
  • the size composition contains a biocide in order to prevent bacterial infestation and thus to avoid a negative influence on the rheology of the size and the binding force of the binding agent.
  • the carrier liquid contained in the sizing composition is essentially formed from water in relation to its weight, that is to say the sizing composition according to the invention is provided in the form of a so-called water sizing agent.
  • biocides examples include formaldehyde, formaldehyde releasers, 2-methyi-4-isothiazolin-3-one (MIT), 5-chloro-2-methyl-4-iosthiazolin-3-one (CIT), 1, 2-Ben - ziothiazolin-3-one (BIT) and biocidal substances that contain bromine and nitrile groups.
  • the biocides are usually used in an amount from 10 to 1000 ppm, preferably from 50 to 500 ppm, based on the weight of the ready-to-use size composition.
  • the size composition can be prepared by adding water and breaking up a clay that acts as an adjusting agent using a high-shear stirrer. Then the refractory base material, pigments (if available) and dyes (if available) are stirred in until a homogeneous mixture is obtained. Finally, wetting agents (if any), anti-foam agents (if any), biocides (if any) and binding agents (if any) are stirred in.
  • the size composition can be produced and sold as a ready-to-use formulated size composition.
  • the size composition can, however, also be produced and marketed in concentrated form. In this case, in order to provide a ready-to-use size composition, the amount of (further) carrier liquid is added which is necessary to set the desired viscosity and density of the size composition.
  • the dry layer thickness of the cover layer is, for example, 0.01 mm to 1 mm, preferably 0.05 mm to 0.8 mm, more preferably 0.1 mm to 0.6 mm and most preferably 0.2 mm to 0.3 mm .
  • the dry layer thickness of the coating is determined either by dimensioning bending bars before and after finishing (dried) with a micrometer screw (preferred) or by measuring with the wet layer thickness comb. For example, you can use a comb to determine the layer thickness by scratching away the coating at the end marks of the comb until the substrate appears. The layer thickness can then be read from the markings on the teeth. Instead, you can also measure the wet layer thickness in the matted state in accordance with DIN EN ISO 2808.
  • the methods according to the invention are suitable per se for the production of all casting molds customary for metal casting, that is for example for cores and molds. Casting molds which comprise very thin-walled sections can also be produced particularly advantageously.
  • the casting molds produced with the molding material mixture or with the method according to the invention have a high level of strength immediately after production and in the entire production process, in particular the sizing-drying process, without the strength of the casting mold being impaired after curing or after sizing. Drying is so high that demolding difficulties occur after the production of the casting when removing the casting mold.
  • these casting molds in the unsized and sized state have a high level of stability with increased air humidity, ie the casting molds can surprisingly also be stored for a long time without problems and without any loss of quality.
  • the casting mold has a very high stability under mechanical stress, so that even thin-walled sections of the casting mold can be realized without them being deformed by the metallostatic pressure during casting.
  • the casting mold has the advantage that after metal casting, in particular iron casting, it has significantly improved disintegration properties, which also enable thin-walled sections of the casting mold to be cored.
  • the invention therefore also relates to a casting mold which was obtained by the method according to the invention described above.
  • Georg Fischer test bars were produced for testing a molding material mixture.
  • Georg Fischer test bars are to be understood as rectangular test bars with dimensions of 180 mm x 22.36 mm x 22.36 mm.
  • the compositions of the molding mixtures are given in Table 1.
  • the following procedure was used to manufacture the Georg Fischer test bars: • The components listed in Table 1 were mixed in a laboratory paddle mixer HSM10 (HOBART GmbH, Hürth, DE). First the quartz sand was initially introduced and particulate amorphous SiO 2 and possibly powdery oxidic boron compounds and / or powdery phosphate-containing compounds were added to it. The mixture was mixed for one minute. A sodium water glass that contained potassium was used as the water glass.
  • the module is therefore given as SiO 2 : M 2 O, where M is the sum of sodium and potassium.
  • M is the sum of sodium and potassium.
  • the molding material mixtures were transferred to the storage bunker of an L1 laboratory hot box core shooting machine from Lämpe & Mösner GmbH (Schopfheim, DE), the mold of which was heated to 180 ° C.
  • test bars 180 mm x 22.36 mm x 22.36 mm
  • test bars 180 mm x 22.36 mm x 22.36 mm
  • standard measuring program “Rg1v_B 870 N / cm” 2 “(3-point bending device) from Multiserw-Morek (Bresnrtz, PL).
  • the flexural strengths were measured according to the following scheme:
  • the parameters of the size composition used were set for the purpose provided here, the application to test cores by means of an immersion application or an immersion bath.
  • the density of the ready-to-use size composition given in Table 3 was measured in accordance with the standard test method DIN EN ISO 2811-2: 2011.
  • the flow time of the ready-to-use size composition given in Table 3 was measured in accordance with the standard test method DIN 53211 (1974) by determination with the DIN cup 4.
  • Table 1 Composition of the molding material mixture.
  • KERNTOP® V 302/88 Parameters of the ready-to-use size KERNTOP® V 302/88 used.
  • KERNTOP® V 302/88 is a water-based coating based on aluminum silicate and graphite, solid approx. 49% by weight. Viscosity 12 Pa-s (at 25 ° C).
  • test cores were immersed one hour after core production with the size composition according to Table 3 at room temperature (25 ° C) by dipping (1 s immersion, 3 s holding time in the size composition, 1 s immersion) coated (finished).
  • the wet layer thickness of the size was adjusted to about 250 mm.
  • test cores were then dried under the conditions specified below (20 min, 140 ° C.) in a forced-air oven and the changes in their flexural strength under the drying conditions were examined in each case.
  • test cores were each dried over a period of 20 minutes, their flexural strengths (In N / cm 2 , according to the definition as given in the leaflet R202 of the Association of German Foundry Experts, October 1987 edition) at various times during the drying, and then again one hour after the end of the drying process, measurements were taken with a standard bending device of the type “MultiservwMorek LRu-2e”, evaluated in accordance with the standard measurement program (3-point flexural strength).
  • Table 4 shows the strength values for the investigated sized test cores, produced with the molding compounds 1.1-1.4. and the sizing according to Table 3.
  • the cold strength of the unsized cores, the minimum strength during the sizing drying process (absolute value) and the relatively largest drop in strength during the sizing drying process are compared.
  • the cold strengths of the sized test cores are listed.
  • Table 4 Absolute flexural strengths before and after the size-drying process as well as the minimum flexural strengths (based on the cold strengths, unsized) during the size-drying process (20 min, 140 ° C).

Abstract

L'invention concerne des moules de fonderie poteyés pour la coulée de métaux pouvant être obtenus à partir de mélanges de matières à mouler à base de liants inorganiques contenant au moins un composé phosphaté et au moins un composé d'oxyde de bore, en particulier des moules et des noyaux poteyés, silicatés, comprenant au moins une matière de base à mouler réfractaire, du verre soluble comme liant inorganique et de la silice amorphe particulaire, ainsi qu'un ou plusieurs composés d'oxyde de bore pulvérulents et un ou plusieurs composés phosphatés. L'invention concerne en outre un procédé pour fabriquer des corps de moules de fonderie poteyés et leur utilisation, en particulier pour la fabrication de pièces moulées constituées d'alliages de fer. L'agent de poteyage est un agent de poteyage à base d'eau.
EP20740224.9A 2019-06-19 2020-06-18 Moules de fonderie poteyés pouvant être obtenus à partir d'un mélange de matières à mouler contenant un liant inorganique et des composés phosphatés et des composés d'oxyde de bore et procédé pour les fabriquer et leur utilisation Pending EP3986634A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102019116702.7A DE102019116702A1 (de) 2019-06-19 2019-06-19 Geschlichtete Gießformen erhältlich aus einer Formstoffmischung enthaltend ein anorganisches Bindemittel und Phosphat- und oxidische Borverbindungen, ein Verfahren zu deren Herstellung und deren Verwendung
PCT/DE2020/100518 WO2020253917A1 (fr) 2019-06-19 2020-06-18 Moules de fonderie poteyés pouvant être obtenus à partir d'un mélange de matières à mouler contenant un liant inorganique et des composés phosphatés et des composés d'oxyde de bore et procédé pour les fabriquer et leur utilisation

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EP3986634A1 true EP3986634A1 (fr) 2022-04-27

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EP20740224.9A Pending EP3986634A1 (fr) 2019-06-19 2020-06-18 Moules de fonderie poteyés pouvant être obtenus à partir d'un mélange de matières à mouler contenant un liant inorganique et des composés phosphatés et des composés d'oxyde de bore et procédé pour les fabriquer et leur utilisation

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US (1) US20220355365A1 (fr)
EP (1) EP3986634A1 (fr)
JP (1) JP2022539004A (fr)
KR (1) KR20220029667A (fr)
CN (1) CN114080283A (fr)
BR (1) BR112021025517A2 (fr)
DE (1) DE102019116702A1 (fr)
MX (1) MX2021015621A (fr)
WO (1) WO2020253917A1 (fr)

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CN114535499B (zh) * 2021-12-31 2023-06-02 北京航空航天大学宁波创新研究院 铸造用抗吸湿型无机粘结剂粉体及激活液和使用方法
FR3135908A1 (fr) * 2022-05-30 2023-12-01 Safran Noyau soluble pour la fabrication de pièces creuses

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MX2021015621A (es) 2022-04-11
BR112021025517A2 (pt) 2022-05-31
KR20220029667A (ko) 2022-03-08
JP2022539004A (ja) 2022-09-07
WO2020253917A1 (fr) 2020-12-24
CN114080283A (zh) 2022-02-22
US20220355365A1 (en) 2022-11-10
DE102019116702A1 (de) 2020-12-24

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