EP3950168A1 - Melanges de matière à mouler à base de liant inorganique et procédé de production de moules et de noyaux pour la coulee de métaux - Google Patents

Melanges de matière à mouler à base de liant inorganique et procédé de production de moules et de noyaux pour la coulee de métaux Download PDF

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EP3950168A1
EP3950168A1 EP21199894.3A EP21199894A EP3950168A1 EP 3950168 A1 EP3950168 A1 EP 3950168A1 EP 21199894 A EP21199894 A EP 21199894A EP 3950168 A1 EP3950168 A1 EP 3950168A1
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EP
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Prior art keywords
weight
material mixture
mold
molding material
phosphate
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EP21199894.3A
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German (de)
English (en)
Inventor
Dennis BARTELS
Heinz DETERS
Antoni Gieniec
Diether Koch
Hannes LINCKE
Martin Oberleiter
Oliver Schmidt
Carolin WALLENHORST
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ASK Chemicals GmbH
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ASK Chemicals GmbH
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Publication of EP3950168A1 publication Critical patent/EP3950168A1/fr
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    • 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
    • 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
    • B22C1/181—Cements, oxides or clays
    • 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
    • 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
    • B22C9/12—Treating moulds or cores, e.g. drying, hardening

Definitions

  • the invention relates to molding material mixtures based on inorganic binders for the production of molds and cores for metal casting, consisting of at least one refractory basic mold material, an inorganic binder and particulate amorphous silicon dioxide as an additive. Furthermore, the invention relates to a method for producing molds and cores using the mold material mixtures.
  • Casting molds are essentially made up of molds or molds and cores, which represent the negative molds of the casting to be produced.
  • These cores and molds consist of a refractory material, for example quartz sand, and a suitable binder that gives the casting mold sufficient mechanical strength after it has been removed from the mold.
  • 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 binder creates a solid bond between the particles of the basic molding material, so that the casting mold has the required mechanical stability.
  • molds form the outer wall for the casting, cores are used to form cavities within the casting. It is not absolutely necessary that molds and cores are made of the same material. In chill casting, for example, the external shaping of the castings is carried out with the help of permanent metal moulds. It is also possible to combine molds and cores that have been produced from mold material mixtures with different compositions and using different processes. If, for the sake of simplicity, only molds are mentioned below, the statements also apply to cores that are based on the same mold material mixture and were manufactured using the same process.
  • Both organic and inorganic binders can be used to produce molds and can be hardened by cold or hot processes.
  • Cold processes are processes that are carried out essentially without heating the mold used to produce the core, usually at room temperature or at a temperature caused by a possible reaction.
  • the curing takes place, for example, in that a gas is passed through the mold material mixture to be cured, thereby triggering a chemical reaction.
  • the mold material mixture is heated after shaping, e.g. by the heated mold, to a sufficiently high temperature to expel the solvent contained in the binder and/or to initiate a chemical reaction that hardens the binder.
  • organic binders Due to their technical properties, organic binders currently have greater importance in the market. Irrespective of their composition, however, they have the disadvantage that they decompose during pouring and sometimes emit considerable amounts of pollutants such as benzene, toluene and xylenes. In addition, the casting of organic binders usually leads to odor and smoke nuisance. In some systems, undesirable emissions even occur during core manufacture and/or storage. Even if the emissions have been reduced over the years through the development of binders, they cannot be completely avoided with organic binders. For this reason, research and development work has turned back to inorganic binders in recent years in order to further improve these and the product properties of the molds and cores produced in this way.
  • CO 2 hardening is used, for example, in GB634817 described, curing by means of hot air without the addition of CO 2 , for example in H. Polzin, W. Tilch and T. Kooyers, G easilyerei-Praxis 6/2006, p. 171.
  • a further development of CO 2 curing by subsequent rinsing with air is in DE 102012103705.1 disclosed. Ester hardening is off, for example GB1029057 known (so-called no-bake method).
  • particulate synthetic amorphous SiO 2 is added to the mold material mixture to increase the strength.
  • EP1802409 and DE 102012103705.1 it is proposed to add amorphous silicon dioxide to the mold material mixtures.
  • the task of the SiO 2 is to improve the decomposition of the cores after thermal stress, for example after casting.
  • EP 1802409 B1 and DE 102012103705.1 it is explained in detail that the addition of synthetic particulate amorphous SiO 2 causes a significant increase in strength.
  • EP 2014392 B1 it is proposed to add a suspension of amorphous, spherical SiO 2 to the mold material mixture, consisting of mold material, caustic soda, binder based on alkali silicate and additives, with the SiO 2 being present in two grain size classifications. With this measure, good flowability, high flexural strength and a high curing speed should be obtained.
  • the object of the present invention is to further improve the properties of inorganic binders, also in order to make them even more universally applicable and to make them an even better alternative to the currently dominant organic binders.
  • molding material mixtures that allow cores with complex geometries to be produced due to further improved strength and/or improved compaction or, in the case of simpler core geometries, to reduce the amount of binder and/or shorten curing times.
  • amorphous silicon dioxides there are types which differ significantly from the others in their effect as an additive to the binder. If particulate amorphous SiO 2 is used as an additive, which was produced by thermal decomposition of ZrSiO 4 to form ZrO 2 and SiO 2 and essentially complete or partial removal of the ZrO 2 , it is found that with identical amounts added and under identical reaction conditions Surprisingly significantly improved strength and / or that the core weight is higher than when using in the EP 1802409 B1 mentioned particulate amorphous SiO 2 from other production processes. The increase in core weight with the same outer dimensions of the core is accompanied by a reduction in gas permeability, which indicates denser packing of the molding material particles.
  • the particulate amorphous SiO 2 produced by the above method is also identified by the term "artificially produced amorphous SiO 2".
  • the particulate amorphous SiO 2 can also be described cumulatively or as an alternative to production by the following parameters.
  • the procedure is generally such that the refractory mold base material is introduced and then the binder and the additive are added together or one after the other while stirring. It is of course also possible to first add all or part of the components and then and/or during this time to stir.
  • the binder is preferably charged before the additive. It is stirred until an even distribution of the binder and the additive in the basic mold material is guaranteed.
  • the mold material mixture is then brought into the desired shape.
  • Standard methods are used for shaping.
  • the mold material mixture can be shot into the mold using a core shooter with the aid of compressed air.
  • Another option is to let the mold material mixture flow freely from the mixer into the mold and compact it there by shaking, tamping or pressing.
  • the molding material mixture is cured using the hot box process, ie it is cured with the aid of hot tools.
  • the hot tools preferably have a temperature of 100 to 300°C, particularly preferably 120°C to 250°C.
  • a gas eg, CO 2 or CO 2 -enriched air
  • the above process (hot box process) is preferably carried out in a core shooter.
  • curing can also take place in that CO 2 , a CO 2 / gas mixture (e.g. with air) or CO 2 and a gas / gas mixture (e.g. air) one after the other (as in detail in UK 102012103705 described) is passed through the cold mold or through the mold material mixture contained therein, the term "cold” meaning temperatures below 100° C., preferably below 50° C. and in particular at room temperature (eg 23° C.).
  • the gas or gas mixture passed through the mold or through the molding material mixture can preferably be slightly heated, ie up to a temperature of 120°C, preferably up to 100°C, particularly preferably up to 80°C.
  • base material(s) Materials customary for the manufacture of casting molds can be used as the refractory base material (hereinafter referred to as base material(s) for short).
  • base material(s) quartz, zirconium or chrome ore sand, olivine, vermiculite, bauxite and fireclay are suitable. It is not necessary to use only new sand. In order to conserve resources and avoid landfill costs, it is even advantageous to use as high a proportion of regenerated used sand as possible.
  • the average diameter of the basic mold materials is generally between 100 ⁇ m and 600 ⁇ m, preferably between 120 ⁇ m and 550 ⁇ m and particularly preferably between 150 ⁇ m and 500 ⁇ m.
  • the particle size can be determined, for example, by sieving according to DIN 66165 (Part 2).
  • artificial molding materials can also be used as basic molding materials, in particular as an additive to the above basic molding materials, but also as an exclusive basic molding material, such as glass beads, glass granules, the spherical ceramic basic molding materials known under the name "Cerabeads” or “Carboaccucast” or hollow aluminum silicate microspheres (so-called microspheres ).
  • Such hollow aluminum silicate microspheres are marketed, for example, by Omega Minerals Germany GmbH, Norderstedt, under the name “Omega Spheres”.
  • Corresponding products are also available from PQ Corporation (USA) under the name “Extendospheres”.
  • the preferred proportion of the artificial basic molding materials is at least about 3% by weight, particularly preferably at least about 5% by weight, particularly preferably at least about 10% by weight, preferably at least about 15% by weight, particularly preferably at least about 20% % by weight, in each case based on the total amount of the refractory basic molding material.
  • the molding material mixture according to the invention comprises an inorganic binder , for example based on water glass.
  • an inorganic binder for example based on water glass.
  • Conventional water glasses such as those previously used as binders in molding material mixtures can be used as the water glass.
  • These water glasses contain dissolved alkali silicates and can be produced by dissolving vitreous lithium, sodium and potassium silicates in water.
  • the water glasses preferably have a molar SiO 2 /M 2 O modulus in the range from 1.6 to 4.0, in particular from 2.0 to less than 3.5, where M is lithium, sodium or potassium.
  • the water glasses have a solids content in the range from 25 to 65% by weight, preferably from 30 to 60% by weight.
  • the solids content refers to the amount of SiO 2 and M 2 O contained in the water glass.
  • between 0.5% by weight and 5% by weight of the binder based on water glass are used, preferably between 0.75% by weight and 4% by weight, particularly preferably between 1% by weight and 3% by weight. 5% by weight, in each case based on the basic molding material.
  • the percentage by weight relates to water glasses with a solids content as indicated above, i.e. includes the diluent.
  • water glass binders those based on water-soluble phosphate glasses and/or borates can also be used, such as those described in U.S. 5,641,015 to be discribed.
  • the preferred phosphate glasses have a solubility in water of at least 200 g/L, preferably at least 800 g/L and contain between 30 and 80 mol% P 2 O 5 , between 20 and 70 mol% Li 2 O, Na 2 O or K 2 O, between 0 and 30 mol% CaO, MgO or ZnO and between 0 and 15 mol% Al 2 O 3 , Fe 2 O 3 or B 2 O 3 .
  • the particularly preferred composition is 58 to 72% by weight P 2 O 5 , 28 to 42% by weight Na 2 O and 0 to 16% by weight CaO.
  • the phosphate anions are preferably present as chains in the phosphate glasses.
  • the phosphate glasses are usually used as approximately 15 to 65% by weight, preferably as approximately 25 to 60% by weight, aqueous solutions. However, it is also possible to add the phosphate glass and the water to the basic molding material separately, with at least part of the phosphate glass dissolving in the water during the production of the molding material mixture.
  • Typical added amounts of the phosphate glass solutions are 0.5% by weight to 15% by weight, preferably between 0.75% by weight and 12% by weight, particularly preferably between 1% by weight and 10% by weight, in each case based on the basic mold material .
  • the specification relates to phosphate glass solutions with a solids content as specified above, i.e. includes the diluent.
  • the mold material mixtures preferably also contain hardeners which cause the mixtures to harden without heat being supplied or a gas having to be passed through the mixture.
  • hardeners can be liquid or solid, organic or inorganic in nature.
  • Suitable organic hardeners include esters of carbonic acid such as propylene carbonate, esters of monocarboxylic acids having 1 to 8 carbon atoms with mono-, di- or trifunctional alcohols such as ethylene glycol diacetate, glycerol mono-, di- and -triacetic acid ester, and cyclic esters of hydroxycarboxylic acids such as for example ⁇ -butyrolactone.
  • esters of carbonic acid such as propylene carbonate
  • esters of monocarboxylic acids having 1 to 8 carbon atoms with mono-, di- or trifunctional alcohols such as ethylene glycol diacetate, glycerol mono-, di- and -triacetic acid ester
  • cyclic esters of hydroxycarboxylic acids such as for example ⁇ -butyrolactone.
  • the esters can also be used mixed with one another.
  • Suitable inorganic hardeners for binders based on water glass are, for example, phosphates such as Lithopix P26 (an aluminum phosphate from Zschimmer und Schwarz GmbH & Co KG Chemische Fabriken) or Fabutit 748 (an aluminum phosphate from Chemische Fabrik Budenheim KG).
  • phosphates such as Lithopix P26 (an aluminum phosphate from Zschimmer und Schwarz GmbH & Co KG Chemische Fabriken) or Fabutit 748 (an aluminum phosphate from Chemische Fabrik Budenheim KG).
  • the ratio of hardener to binder can vary depending on the desired property, e.g. processing time and/or stripping time of the molding mixture.
  • the proportion of hardener (weight ratio of hardener to binder and, in the case of water glass, the total mass of the silicate solution or other binders taken up in the middle of the solution) is advantageously 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 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 mold material mixtures contain a proportion of an artificially produced particulate amorphous SiO 2 , this originating from the process of thermal decomposition of ZrSiO 4 to form ZrO 2 and SiO 2 .
  • the inventors assume that the improved flowability is based on the fact that the particulate amorphous SiO 2 used according to the invention has less tendency to agglomerate than the amorphous SiO 2 from the other production processes and therefore already without the effect of strong shearing forces more primary particles are present.
  • the SiO 2 according to the invention has more isolated particles than in the comparison ( 2 ).
  • a stronger intergrowth of individual spheres into larger associations which can no longer be broken up into the primary particles.
  • the two figures indicate that the primary particles of the SiO 2 according to the invention have a broader grain size distribution than in the prior art, which can also contribute to improved flowability.
  • the particle size was determined using dynamic light scattering on a Horiba LA 950, the scanning electron microscope images using an ultra-high-resolution Nova NanoSem 230 scanning electron microscope from FEI, which was equipped with a through-the-lens detector (TLD).
  • TLD through-the-lens detector
  • the samples were dispersed in distilled water and then applied to an aluminum holder covered with copper tape before the water was evaporated. In this way, details of the primary particle shape down to the order of 0.01 ⁇ m could be made visible.
  • the amorphous SiO 2 originating from the ZrSiO 4 process can still contain zirconium compounds, especially ZrO 2 .
  • the zirconium content, calculated as ZrO 2 is usually below approx. 12% by weight, preferably below approx. 10% by weight, particularly preferably below approx. 8% by weight and particularly preferably below approx. 5% by weight .% and on the other hand greater than 0.01% by weight, greater than 0.1% by weight, or even greater than 0.2% by weight.
  • Fe 2 O 3 , Al 2 O 3 P 2 O 5 , HfO 2 , TiO 2 , CaO, Na 2 O and K 2 O with a total content of less than approx. 8% by weight, preferably less than approx. 5% by weight and more preferably less than about 3% by weight.
  • the water content of the particulate amorphous SiO 2 used according to the invention is less than 10% by weight, preferably less than 5% by weight and particularly preferably less than 2% by weight.
  • the amorphous SiO 2 is used as a pourable dry powder.
  • the powder is free-flowing and pourable under its own weight.
  • the average particle size of the particulate amorphous SiO 2 is preferably 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, primary particles with diameters between approx. 0.01 ⁇ m and approx. 5 ⁇ m were found. The determination was made using dynamic light scattering on a Horiba LA 950.
  • the particulate amorphous silicon dioxide has an average particle size of preferably less than 300 ⁇ m, preferably less than 200 ⁇ m, particularly preferably less than 100 ⁇ m.
  • the particle size can be determined by sieve analysis.
  • the sieve residue of the particulate amorphous SiO 2 when passing through a sieve with a mesh size of 125 ⁇ m (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% by weight. %.
  • the sieving residue is determined according to the machine sieving method described in DIN 66165 (Part 2), with a chain ring also being used as a sieving aid.
  • the residue of particulate amorphous SiO 2 used according to the invention is not more than approx. 10% by weight, particularly preferably not more than approx 5% by weight and very particularly preferably not more than about 2% by weight (sieving according to DIN ISO 3310).
  • the ratio of primary particles (non-agglomerated, non-fused and non-fused particles) to the secondary particles (agglomerated, non-fused and/or fused particles including particles which (clearly) do not have a spherical shape) of the particulate amorphous SiO 2 can be determined by means of scanning electron micrographs. These recordings were made using an ultra-high-resolution Nova NanoSem 230 scanning electron microscope from FEI, which was equipped with a through-the-lens detector (TLD).
  • TLD through-the-lens detector
  • the samples were dispersed in distilled water and then placed on an aluminum holder covered with copper tape before the water was evaporated. In this way, details of the primary particle shape down to 0.01 ⁇ m could be made visible.
  • the percentage recording is based on a statistical evaluation of a large number of SEM images, such as those in Fig.1 and Fig.2 are shown, whereby agglomeration / intergrowth / fusion can only be classified as such if the respective contours of individual adjacent spherical (converging) primary particles can no longer be recognized.
  • the classification is made as primary particles, even if the view does not allow an actual classification due to the two-dimensional nature of the recordings.
  • the area only the visible particle areas are evaluated and contribute to the total.
  • Suitable particulate amorphous SiO 2 used according to the invention has a BET of less than or equal to 35 m 2 /g, preferably less than or equal to 20 m 2 /g, particularly preferably less than or equal to 17 m 2 /g and particularly preferably less than or equal to 15 m 2 /g.
  • the lower limits are greater than or equal to 1 m 2 /g, preferably greater than or equal to 2 m 2 /g, particularly preferably greater than or equal to 3 m 2 /g and particularly preferably greater than or equal to 4 m 2 /g.
  • the particulate amorphous SiO 2 are used, preferably between 0.1% by weight and 1.8% by weight and particularly preferably between 0.1% by weight % and 1.5% by weight, based in each case on the basic molding material.
  • the ratio of inorganic binder to particulate amorphous SiO 2 used according to the invention can be varied within wide limits. This offers the possibility of greatly varying the initial strength of the cores, ie the strength immediately after removal from the mold, without significantly influencing the final strength. This is of great interest, especially in light metal casting. On the one hand, high initial strengths are desired here so that the cores can be transported without problems after production or assembled into whole core packages, on the other hand the final strengths should not be too high in order to avoid problems when the core disintegrates after casting.
  • the particulate amorphous SiO 2 is preferably contained in a proportion of 2% by weight to 60% by weight, particularly preferably from 3% by weight to 55% by weight and entirely more preferably from 4% to 50% by weight.
  • the artificially produced (particulate) amorphous SiO 2 corresponds to the particulate amorphous SiO 2 according to the terminology of the claims and is used in particular as a powder, in particular with a water content of less than 5% by weight, preferably less than 3% by weight, in particular less than 2% by weight. %, (water content determined according to Karl Fischer). Irrespective of this, the ignition loss (at 400° C.) is preferably less than 6, less than 5 or even less than 4% by weight.
  • the particulate amorphous SiO 2 used according to the invention can be added both before and after or mixed together with the addition of the binder directly to the refractory material.
  • the particulate amorphous SiO 2 used according to the invention is preferably added directly to the refractory material in dry and powder form after the addition of the binder.
  • a premix of the SiO 2 is first prepared with an aqueous alkaline solution, such as caustic soda, and optionally the binder or a part of the binder, and this is then mixed into the refractory basic molding material.
  • an aqueous alkaline solution such as caustic soda
  • the binder or proportion of binder that may still be present but not used for the premix can be added to the basic molding material before or after the addition of the premix or together with it.
  • a non-inventive synthetic particulate amorphous SiO 2 in addition to the particulate amorphous SiO 2 a non-inventive synthetic particulate amorphous SiO 2 according to EP 1802409 B1 be used in a ratio of 1 to less than 1, for example.
  • inventive and non-inventive SiO 2 can be advantageous when the effect of the particulate amorphous SiO 2 is to be “weakened”.
  • inventive and non-inventive amorphous SiO 2 to the mold material mixture allow the strength and/or compaction of the casting molds to be adjusted in a targeted manner.
  • the molding material mixture according to the invention can, in a further embodiment, comprise a phosphorus-containing compound.
  • a phosphorus-containing compound is preferred in the case of very thin-walled sections of a casting mold and in particular in the case of cores, since in this way the thermal stability of the cores or the thin-walled section of the casting mold can be increased. This is particularly important when the liquid metal hits a sloping surface during casting and exerts a strong erosive effect there due to the high metallostatic pressure or can lead to deformations, particularly of thin-walled sections of the casting mold.
  • Suitable phosphorus compounds do not or not significantly affect the processing time of the molding mixtures according to the invention.
  • An example of this is sodium hexametaphosphate.
  • Other suitable representatives and their addition amounts are in the WO 2008/046653 described in detail and this is also made to the disclosure of the present property rights.
  • the molding material mixtures according to the invention already have improved flowability compared to the prior art, if desired, this can be increased even further by adding flake-form lubricants, for example to completely fill molds with particularly narrow passages.
  • the mold material mixture according to the invention contains a proportion of flake-form lubricants, in particular graphite or MoS 2 .
  • the amount of the added flake-form lubricant, in particular graphite is preferably 0.05% by weight to 1% by weight, based on the basic mold material.
  • the molding material mixture according to the invention can also include other additives.
  • release agents can be added, which facilitate the detachment of the cores from the mold.
  • suitable release agents are calcium stearate, fatty acid esters, waxes, natural resins or special alkyd resins. If these release agents are soluble in the binder and do not separate from it even after prolonged storage, especially at low temperatures, they can already be contained in the binder component, but they can also represent part of the additive or be added to the molding mixture as a separate component .
  • Organic additives can be added to improve the cast surface.
  • Suitable organic additives are, for example, phenol-formaldehyde resins such as novolaks, epoxy resins such as bisphenol A epoxy resins, bisphenol F epoxy resins or epoxidized novolaks, polyols such as polyethylene or polypropylene glycols, glycerol or polyglycerol, polyolefins such as polyethylene or polypropylene, copolymers Olefins such as ethylene and/or propylene with other comonomers such as vinyl acetate or styrene and/or diene monomers such as butadiene, polyamides such as polyamide 6, polyamide 12 or polyamide 6,6, natural resins such as gum resin, fatty acid esters such as cetyl palmitate, fatty acid amides such as ethylenediamine bisstearamide, metal soaps such as stearates or oleates of divalent or trivalent metals, and carbohydrates such as de
  • Carbohydrates in particular dextrins, are particularly suitable. Suitable carbohydrates are in the WO 2008/046651 A1 described.
  • the organic additives can be used either as a pure substance or in a mixture with various other organic and/or inorganic compounds.
  • the organic additives are preferably used in an amount of 0.01% by weight to 1.5% by weight, more preferably 0.05% by weight to 1.3% by weight and most preferably 0.1% by weight to 1 % by weight added, in each case based on the molding material.
  • silanes can also be added to the mold material mixture according to the invention in order to increase the resistance of the cores to high atmospheric humidity and/or to water-based mold material coatings.
  • the molding material mixture according to the invention therefore contains a proportion of at least one silane.
  • suitable silanes are aminosilanes, epoxysilanes, mercaptosilanes, hydroxysilanes and ureidosilanes.
  • silanes examples include ⁇ -aminopropyl-trimethoxysilane, ⁇ -hydroxypropyl-trimethoxysilane, 3-ureidopropyl-trimethoxysilane, ⁇ -mercaptopropyl-trimethoxysilane, ⁇ -glycidoxypropyl-trimethoxysilane, ⁇ -(3,4-epoxycyclohexyl)-trimethoxysilane, N- ⁇ -(Aminoethyl)- ⁇ -aminopropyl-trimethoxysilane and their triethoxy-analogous compounds.
  • the silanes mentioned, in particular the aminosilanes can also be prehydrolyzed. Based on the binder, typically about 0.1% by weight to 2% by weight of silane is used, preferably about 0.1% by weight to 1% by weight.
  • alkali metal siliconates for example potassium methyl siliconate, of which about 0.5% by weight to about 15% by weight, preferably about 1% by weight to about 10% by weight and particularly preferably about 1% by weight up to approx. 5% by weight, based on the binder, can be used.
  • the molding material mixture includes an organic additive, it can be added at any time during the production of the molding material mixture.
  • the addition can take place in bulk or else in the form of a solution
  • Water-soluble organic additives can be used in the form of an aqueous solution. If the organic additives are soluble in the binder and can be stored in it for several months without decomposing, they can also be dissolved in the binder and thus added to the molding material together with it. Water-insoluble additives can be used in the form of a dispersion or a paste. The dispersions or pastes preferably contain water as the liquid medium.
  • the mold material mixture contains silanes and/or alkali metal siliconates, they are usually added in the form of being worked into the binder beforehand. However, they can also be added to the mold material as a separate component.
  • Inorganic additives can also have a positive effect on the properties of the molding material mixtures according to the invention.
  • Vol 89, pp 47 - 54 (1981 ) carbonates mentioned the moisture resistance of the cores during storage
  • Alkali borates as components of water glass binders are used, for example, in EP0111398 disclosed.
  • Suitable inorganic additives to improve the casting surface based on BaSO 4 are in DE 102012104934.3 described and can be added to the mold material mixture as a complete or at least partial replacement of the organic additives mentioned above.
  • the cores produced from these molding material mixtures disintegrate well after casting, particularly in aluminum casting.
  • the use of the cores produced from the molding material mixtures according to the invention is not limited to light metal casting.
  • the casting molds are generally suitable for casting metals. Such metals are, for example, also non-ferrous metals such as brass or bronze, as well as ferrous metals.
  • Silica sand was placed in the bowl of a Hobart mixer (model HSM 10). The binder was then added with stirring and mixed intensively with the sand for 1 minute each time. The sand used, the type of binder and the amounts added are listed in Table 1.
  • the mold material mixtures were introduced into the mold from the storage bunker using compressed air (5 bar).
  • the residence time in the hot tool for curing the mixtures was 35 seconds.
  • hot air (2 bar, 100°C when entering the tool) was passed through the mold during the last 20 seconds.
  • the mold was opened and the test bar was removed.
  • the test specimens for determining the core weights are produced using this method.
  • test bars were placed in a Georg Fischer strength tester equipped with a 3-point bending device, and the force which caused the test bars to break was measured.
  • Table 2 shows that the production method of the artificially produced particulate amorphous SiO 2 has a significant influence on the properties of the cores.
  • the cores that were produced with an inorganic binder and the SiO 2 according to the invention have higher strengths and higher core weights than the cores that contain the SiO 2 not according to the invention.
  • Examples 1.5 and 1.6 show that the positive effects are not based on the presence of ZrO 2 in the amorphous SiO 2 according to the invention originating from the ZrSO 4 process.
  • the molding material mixtures were analogous to 1.1.1. manufactured. Their compositions are listed in Table 3. ⁇ b>Table 3 ⁇ /b> (experiment 2) Composition of the molding material mixtures # basic molding material [GT] Binder [GT] amorphous SiO 2 [GT] Surfactant [GT] 2.1 100 a) 2.0d ) 0.5f ) not according to the invention 2.2 100 a) 2.0e ) 1.0g ) not according to the invention 2.3 100 a) 2.0d ) 0.5 hours) according to the invention 2.4 100 b) 2.0d ) 0.5 f) not according to the invention 2.5 100 b) 2.0d ) 0.5 hours) according to the invention 2.6 100c) 2.0d ) 0.5f ) not according to the invention 2.7 100 c) 2.0d ) 0.5 hours) according to the invention 2.8 100 a) 2.0d ) 0.5f ) 0.04 i) not according to the invention 2.9 100 a) 2.0d ) 0.5 hours) 0.04 i) according to the invention
  • inlet channel cores were produced which are larger and have a more complex geometry than the Georg Fischer bars ( 3 ).
  • the mold material mixtures were transferred to the storage bunker of an L 6.5 core shooter from Röperwerk-G manmaschinen GmbH, Viersen, DE, whose mold was heated to 180° C., and from there introduced into the mold by means of compressed air.
  • the pressures used are listed in Table 4.
  • the residence time in the hot tool for curing the mixtures was 35 seconds.
  • hot air (2 bar, 150°C when entering the tool) was passed through the mold during the last 20 seconds.
  • the mold was opened and the test bar was removed.
  • Table 4 confirms the improved flowability of the molding material mixtures according to the invention compared to the prior art on the basis of a core from foundry practice. The positive effect is independent of the type of sand and the shooting pressure.
  • the molding material mixtures were produced analogously to 1.1.1. Their compositions are given in Table 5. ⁇ b>Table 5 ⁇ /b> (Trial 3) Composition of the molding material mixtures # Quartz sand H 32 a) [GT] Binder b) [GT] amorphous SiO 2 [GT] separately added ZrO 2 [GT] 3.1 100 2.0 not according to the invention 3.2 100 2.0 0.5 c) not according to the invention 3.3 100 2.0 0.475 c) 0.025g ) not according to the invention 3.4 100 2.0 0.475 c) 0.025h ) not according to the invention 3.5 100 2.0 0.5d ) according to the invention 3.6 100 2.0 0.5e ) according to the invention 3.7 100 2.0 0.5f ) according to the invention a) Quartz Works Frechen GmbH b) alkali water glass; molar modulus about 2.33; Solids content approx.
  • the mold material mixtures were shot from the storage chamber using compressed air (4 bar) into a non-tempered mold with two engravings for round cores with a diameter of 50 mm and a height of 50 mm.
  • CO 2 was first injected for 6 seconds at a CO 2 flow of 2 L/min. and then compressed air at a pressure of 4 bar is passed through the mold filled with the mold material mixture for 45 seconds.
  • the temperatures of both gases were about 23°C when they entered the mold.
  • Tab. 8 lists the gassing times with air. ⁇ b>Table 8 ⁇ /b> (Trial 3) Compressive strengths when cured by CO 2 # gassing time [sec] Instant strength [N/cm 2 ] Strength after 24 hours [N/cm 2 ] 10 12 64 15 20 57 20 24 51 3.1 30 35 44 not according to the invention 45 40 46 60 42 45 90 43 38 10 33 67 15 42 65 20 46 66 3.2 30 49 57 not according to the invention 45 51 54 60 56 52 90 57 48 10 40 93 15 48 94 20 48 95 3.5 30 54 88 according to the invention 45 60 83 60 63 78 90 67 67 67
  • test specimens were removed from the mold and their compressive strengths were determined using a Zwick universal testing machine (model Z 010) immediately, ie a maximum of 15 seconds, after removal.
  • compressive strength of the test specimens was tested after 24 hours, and in some cases also after 3 and 6 days of storage in a climate chamber. Constant storage conditions could be ensured with the aid of a climate chamber (Rubarth Apparate GmbH).
  • a temperature of 23°C and a relative humidity of 50% were set.
  • the values given in the tables are mean values from 8 cores each.
  • the core weights were also determined 24 hours after removal from the core box in the case of combination curing with CO 2 and air. The weighing was carried out on a laboratory balance with an accuracy of 0.1 g.
  • Tables 6 - 9 show that the positive properties of the particulate amorphous SiO 2 used compared to the prior art are not limited to hot curing (Table 2), but also when the molding material mixtures are cured using a combination of CO 2 and air, by means of CO 2 and by means of air can be observed.
  • Quartz sand from Quartzwerke Frechen GmbH was filled into the bowl of a mixer from Hobart (model HSM 10). First the hardener and then the binder were then added with stirring and mixed intensively with the sand for 1 minute each time.
  • composition of the mold material mixtures used to produce the test specimens is listed in Table 10 in parts by weight (pbw).
  • the processing times of the individual mixtures are given in Table 10.
  • AZ stripping time
  • a second part of the respective mixture was poured into a round mold 100 mm high and 100 mm in diameter by hand and also compacted with a hand plate.
  • the surface hardness of the compacted mold material mixture was then tested at specific time intervals using the Georg Fischer surface hardness tester. As soon as a mold material mixture is so hard that the test ball no longer penetrates the core surfaces, the stripping time has been reached.
  • the stripping times for the individual mixtures are given in Table 10.
  • test bars were placed in a Georg Fischer strength tester equipped with a 3-point bending device, and the force which caused the test bars to break was measured.
  • Table 11 shows the positive effects of the particulate amorphous SiO 2 used with regard to strength and core weight during cold hardening using an ester mixture (Ex. 4.1-4.6) or a phosphate hardener (Ex. 4.7-4.11) compared to the prior art.

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EP21199894.3A 2012-10-19 2013-10-18 Melanges de matière à mouler à base de liant inorganique et procédé de production de moules et de noyaux pour la coulee de métaux Pending EP3950168A1 (fr)

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RU2015118399A (ru) 2016-12-10
US10092946B2 (en) 2018-10-09
DE102012020509A1 (de) 2014-06-12
CN104736270B (zh) 2018-10-09
HUE058306T2 (hu) 2022-07-28
KR20150074109A (ko) 2015-07-01
PL2908968T3 (pl) 2022-04-19
BR112015008549A2 (pt) 2017-07-04
WO2014059967A3 (fr) 2014-07-17
US20150246387A1 (en) 2015-09-03
JP2015532209A (ja) 2015-11-09
BR112015008549B1 (pt) 2019-11-19
KR102104999B1 (ko) 2020-06-01
RU2650219C2 (ru) 2018-04-11
CN104736270A (zh) 2015-06-24
JP6397415B2 (ja) 2018-09-26
EP2908968B1 (fr) 2021-11-24
ZA201502169B (en) 2016-01-27
MX371009B (es) 2020-01-13
MX2015004904A (es) 2015-07-21
WO2014059967A2 (fr) 2014-04-24
ES2906237T3 (es) 2022-04-13

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