EP2908968B1 - Formstoffmischungen auf der basis anorganischer bindemittel und verfahren zur herstellung von formen und kerne für den metallguss - Google Patents

Formstoffmischungen auf der basis anorganischer bindemittel und verfahren zur herstellung von formen und kerne für den metallguss Download PDF

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EP2908968B1
EP2908968B1 EP13811773.4A EP13811773A EP2908968B1 EP 2908968 B1 EP2908968 B1 EP 2908968B1 EP 13811773 A EP13811773 A EP 13811773A EP 2908968 B1 EP2908968 B1 EP 2908968B1
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Prior art keywords
material mixture
mold material
mold
weight
phosphate
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German (de)
English (en)
French (fr)
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EP2908968A2 (de
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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Priority to PL13811773T priority Critical patent/PL2908968T3/pl
Priority to EP21199894.3A priority patent/EP3950168A1/de
Publication of EP2908968A2 publication Critical patent/EP2908968A2/de
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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 mixtures based on inorganic binders for the production of molds and cores for metal casting, consisting of at least one refractory mold base material, an inorganic binder and particulate amorphous silicon dioxide as an additive.
  • the invention also relates to a method for producing molds and cores using the molding material mixtures.
  • Casting molds are essentially composed 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 binding agent which 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 binding agent creates a firm 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 the molds and cores are made of the same material. For example, in permanent mold casting, the external shaping of the cast pieces is done with the help of permanent metallic molds. A combination of molds and cores that have been produced from differently composed molding material mixtures and using different processes is also possible. If in the following, for the sake of simplicity, only forms are spoken of, the statements also apply to the same extent to cores that are based on the same molding material mixture and were manufactured using the same process.
  • Both organic and inorganic binders can be used to produce molds, and they can be hardened by cold or hot processes.
  • Cold processes are those processes which are carried out essentially without heating the mold used to manufacture 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 molding material mixture to be cured, thereby triggering a chemical reaction.
  • the molding material mixture is heated to a sufficiently high temperature after molding, e.g. by the heated molding tool, to drive out the solvent contained in the binder and / or to initiate a chemical reaction through which the binder is hardened.
  • organic binders Due to their technical properties, organic binders currently have an economic impact. the greater importance in the market. Regardless of their composition, however, they have the disadvantage that they decompose during casting and in some cases emit considerable quantities 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 through the development of binders over the years, they cannot be completely avoided with organic binders. For this reason, research and development activities in recent years have turned back to inorganic binders in order to further improve these and the product properties of the molds and cores produced in this way.
  • the CO 2 hardening is for example in GB 634817 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 purging with air is in DE 102012103705.1 disclosed.
  • the ester hardening is, for example, off GB 1029057 known (so-called no-bake method).
  • particulate synthetic amorphous SiO 2 is added to the molding material mixture to increase the strength.
  • EP 1802409 and DE 102012103705.1 it is proposed to add amorphous silicon dioxide to each of the molding mixtures.
  • the task of SiO 2 is to improve the decomposition of the cores after a thermal load, 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 molding material mixture, consisting of molding material, sodium hydroxide solution, alkali silicate-based binder and additives, the SiO 2 being present in two grain size classifications. With this measure, a good flowability, high flexural strength and a high curing rate 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 which allow cores with complex geometry to be produced on the basis of further improved strengths and / or improved compaction or, in the case of simpler core geometries, to reduce the amount of binder and / or shorten the curing times.
  • particulate amorphous SiO 2 is used as an additive, which was produced by thermal decomposition of ZrSiO 4 to ZrO 2 and SiO 2 and essentially complete or partial separation of the ZrO 2 , it is found that an identical addition quantity and under identical reaction conditions Surprisingly, it has significantly improved strengths and / or that the core weight is higher than when using the EP 1802409 B1 called particulate amorphous SiO 2 from other production processes.
  • the increase in the core weight with the same external dimensions of the core is accompanied by a decrease in gas permeability, which indicates a closer packing of the molding material particles.
  • the particulate amorphous SiO 2 produced according to the above method is also characterized 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 general procedure is that the refractory molding base material is initially introduced and then the binder and the additive are added together or one after the other with stirring. It is of course also possible to add all or some of the components first and then to stir and / or during this time.
  • the binder is preferably charged before the additive. It is stirred until a uniform distribution of the binder and the additive in the molding material is guaranteed.
  • the molding material mixture is then brought into the desired shape.
  • the usual methods are used for the shaping.
  • the molding material mixture can be shot into the molding tool by means of a core shooter with the aid of compressed air.
  • Another possibility is to let the molding material mixture trickle freely from the mixer into the molding tool and to compress it there by shaking, tamping or pressing.
  • the hardening of the molding material mixture is carried out according to one embodiment of the invention of the hot box process, ie it is cured using hot tools.
  • the hot tools preferably have a temperature of 100 to 300.degree. C., particularly preferably 120.degree. C. to 250.degree.
  • 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 (for example with air) or CO 2 and a gas / gas mixture (for example air) one after the other (as in detail in FIG DE 102012103705 described) is passed through the cold mold or through the molding material mixture contained therein,
  • the term "cold” means temperatures below 100 ° C, preferably below 50 ° C and especially at room temperature (eg 23 ° C).
  • the gas or gas mixture passed through the molding tool or through the molding material mixture can preferably be slightly heated, ie up to a temperature of 120.degree. C., preferably up to 100.degree. C., particularly preferably up to 80.degree.
  • refractory basic molding material for the production of casting molds
  • s refractory basic molding material
  • quartz, zirconium or chrome ore sand, olivine, vermiculite, bauxite and chamotte are suitable. It is not necessary to only use new sand. In the interests of conserving resources and avoiding landfill costs, it is even advantageous to use as high a proportion of regenerated used sand as possible.
  • Regenerated materials obtained by washing and subsequent drying are also suitable.
  • Regenerated material obtained through purely mechanical treatment can also be used.
  • the regrind can make up at least approx. 70% by weight of the basic molding material, preferably at least approx. 80% by weight and particularly preferably at least approx. 90% by weight.
  • the mean 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 molding base materials, in particular as an additive to the above molding base materials, but also as exclusive molding base material, such as glass beads, glass granulate, the spherical ceramic molding materials known under the name “Cerabeads” or “Carboaccucast” or 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 synthetic mold base 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, based in each case on the total amount of the refractory base 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 made 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 2.0 to less than 3.5, where M stands for 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 relates to the amount of SiO 2 and M 2 O contained in the water glass.
  • the waterglass-based binder between 0.5% by weight and 5% by weight of the waterglass-based binder are used, preferably between 0.75% and 4% by weight, particularly preferably between 1% and 3% by weight, 5% by weight, based in each case on the basic molding material.
  • the percentages by weight refer to water glasses with a solids content as stated above, i.e. including the diluent.
  • water glass binders those based on water-soluble phosphate glasses and / or borates can also be used, such as those described in, for example 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 approx. 15 to 65% by weight, preferably as approx. 25 to 60% by weight, aqueous solutions. However, it is also possible to add the phosphate glass and the water separately to the basic molding material, 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 molding material .
  • the information relates to phosphate glass solutions with a solids content as stated above, i.e. includes the diluent.
  • the molding material mixtures preferably also contain hardeners which cause the mixtures to solidify 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 are, for example, esters of carbonic acid such as propylene carbonate, esters of monocarboxylic acids with 1 to 8 carbon atoms with mono-, di- or trifunctional alcohols such as ethylene glycol diacetate, glycerol mono-, di- and triacetic acid esters, and cyclic esters of hydroxycarboxylic acids such as for example ⁇ -butyrolactone.
  • esters of carbonic acid such as propylene carbonate
  • esters of monocarboxylic acids with 1 to 8 carbon atoms with mono-, di- or trifunctional alcohols such as ethylene glycol diacetate, glycerol mono-, di- and triacetic acid esters
  • 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 e.g. 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 material mixtures.
  • 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 absorbed in the solvent) 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 .%, each 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 molding 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 ZrO 2 and SiO 2 .
  • Corresponding products are for example from the companies Possehl Erzarior GmbH, Doral Fused Materials Pty. Ltd., Cofermin Rohscher GmbH & Co.KG and TAM Ceramics LLC (ZrSiO 4 process).
  • 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 manufacturing processes and therefore already without the action of strong shear forces there are more primary particles.
  • Fig. 1 one can see that there are more isolated particles in the SiO 2 according to the invention than in the comparison ( Fig. 2 ).
  • Fig. 2 a stronger coalescence of individual spheres to form larger associations that 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 with the help of dynamic light scattering on a Horiba LA 950, the scanning electron microscope images with the help of an ultra-high-resolution scanning electron microscope Nova NanoSem 230 from FEI, which was equipped with a Through The Lens Detector (TLD).
  • TLD Through The Lens Detector
  • the samples were used for the SEM measurements dispersed in distilled water and then applied to an aluminum holder glued 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 about 12% by weight, preferably below about 10% by weight, particularly preferably below about 8% by weight and particularly preferably below about 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 particularly 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 mean 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, with primary particles with diameters between approx. 0.01 ⁇ m and about 5 ⁇ m were found. The determination was carried out with the aid of dynamic light scattering on a Horiba LA 950.
  • the particulate amorphous silicon dioxide has an average particle size of preferably less than 300 ⁇ m, more 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 125 ⁇ m 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% by weight. %.
  • the sieve residue is determined using 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-grown and non-fused particles) to the secondary particles (agglomerated, co-grown and / or fused particles including the particles which (clearly) do not have a spherical shape) of the particulate amorphous SiO 2 can be determined. These recordings were made with the aid of an ultra-high-resolution scanning electron microscope Nova NanoSem 230 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 detection is based on statistical evaluations of a large number of SEM recordings, such as those in Fig.1 and Fig. 2 are shown, whereby agglomeration / intergrowth / merging is / are only to be classified as such if the respective contours of individual neighboring spherical (intertwining) 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-dimensionality of the recordings.
  • the area only the visible particle areas are evaluated and contribute to the total.
  • Suitable particulate amorphous SiO 2 used in accordance with 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, each based 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 strengths of the cores, ie the strength immediately after removal from the mold, without significantly influencing the final strengths. This is of particular interest in light metal casting. On the one hand, high initial strengths are required here so that the cores can be easily transported or assembled into whole core packages after their production, on the other hand, the final strengths should not be too high in order to avoid difficulties 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 particularly preferably from 4% by weight 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 others 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). Regardless of this, the loss on ignition (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 either before or after or mixed together with the addition of 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 with an aqueous alkali lye, such as sodium hydroxide solution, and optionally the binder or a part of the binder is produced and this is then mixed with the refractory basic molding material.
  • aqueous alkali lye such as sodium hydroxide solution
  • binder or a part of the binder is produced and this is then mixed with the refractory basic molding material.
  • Any binder or binder that may still be present but not used for the premix can be added to the molding base material before or after the addition of the premix or together with it.
  • a synthetic particulate amorphous SiO 2 not according to the invention according to FIG EP 1802409 B1 for example, in a ratio of 1 to less than 1 can be used.
  • Mixtures of SiO 2 according to the invention and SiO 2 not according to the invention can be advantageous if the effect of the particulate amorphous SiO 2 is to be "weakened".
  • amorphous SiO 2 according to the invention and not according to the invention to the molding material mixture, the strengths and / or the densities of the casting molds can 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 for very thin-walled sections of a casting mold and in particular for 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 an inclined surface during casting and there, due to the high metallostatic pressure, exerts a strong erosion effect or can lead to deformations in particular of thin-walled sections of the casting mold.
  • Suitable phosphorus compounds do not, or not significantly, influence the processing time of the molding material mixtures according to the invention.
  • An example of this is sodium hexametaphosphate.
  • Further suitable representatives as well as their added amounts are in the WO 2008/046653 described in detail and this is also made to the disclosure of the present property right.
  • the molding material mixtures according to the invention already have an improved flowability compared to the prior art, this can, if desired, be increased even further by adding platelet-shaped lubricants, for example in order to completely fill molds with particularly narrow passages.
  • the molding material mixture according to the invention contains a proportion of flake-form lubricants, in particular graphite or MoS 2 .
  • the amount of flake-form lubricant added, in particular graphite is preferably 0.05% by weight to 1% by weight, based on the basic molding material.
  • surface-active substances in particular surfactants, can also be used, which likewise further improve the flowability of the molding material mixture according to the invention.
  • the molding material mixture according to the invention can also comprise further additives.
  • release agents can be added which facilitate the removal of the cores from the mold. Suitable release agents are, for example, 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 be part of the additive or be added as a separate component to the molding material mixture .
  • Organic additives can be added to improve the casting 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, glycerin or polyglycerin, polyolefins such as polyethylene or polypropylene, copolymers, for example 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 bivalent or trivalent metal
  • Carbohydrates in particular dextrins, are particularly suitable here. 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, particularly preferably 0.05% by weight to 1.3% by weight and very particularly preferably 0.1% by weight to 1% by weight % By weight added, in each case based on the molding material.
  • silanes can also be added to the molding material mixture according to the invention in order to increase the resistance of the cores to high atmospheric humidity and / or to water-based molding material coatings.
  • the molding material mixture according to the invention therefore contains a proportion of at least one silane.
  • Suitable silanes are, for example, aminosilanes, epoxysilanes, mercaptosilanes, hydroxysilanes and ureidosilanes.
  • silanes examples include ⁇ -aminopropyl-trimethoxysilane, ⁇ -hydroxypropyl-trimethoxysilane, 3-ureidopropyltrimethoxysilane, ⁇ -mercaptopropyl-trimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ - (3,4-epoxycycloherxyl- (aminoethyl) ⁇ -trimethoxy - ⁇ -aminopropyl-trimethoxysilane and their triethoxy-analogous compounds.
  • the silanes mentioned, in particular the aminosilanes can also be prehydrolyzed.
  • silane based on the binder
  • Further suitable additives are alkali metal siliconates, for example potassium methyl siliconate, of which approx. 0.5% by weight to approx. 15% by weight, preferably approx. 1% by weight to approx. 10% by weight and particularly preferably approx. 1% by weight Up to approx. 5% by weight, based on the binder, can be used.
  • the molding material mixture comprises an organic additive
  • it can be added at any point in time during the production of the molding material mixture.
  • the addition can take place in bulk or 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 are stable in storage for several months without decomposition, 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 molding material mixture contains silanes and / or alkali methyl siliconates, they are usually added in the form that they are incorporated into the binder beforehand. However, they can also be added to the molding 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.
  • Alkali borates as components of water glass binders are, for example, in EP 0111398 disclosed.
  • Suitable inorganic additives for improving the casting surface based on BaSO 4 are in DE 102012104934.3 and can be added to the molding material mixture as a complete or at least partial replacement of the organic additives mentioned above.
  • the cores produced from these molding material mixtures show good disintegration after casting, in particular 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 bronzes, as well as ferrous metals.
  • Quartz sand was poured into the bowl of a mixer from Hobart (model HSM 10). The binder was then added while stirring and mixed intensively with the sand for 1 minute.
  • the sand used, the type of binding agent and the respective amounts added are listed in Table 1.
  • particulate amorphous SiO 2 As in 1.1.1.1. process with the difference that after the addition of the binder to the molding material mixture, particulate amorphous SiO 2 was also added and this was also mixed in for 1 minute. The type of particulate amorphous SiO 2 and the amounts added are listed in Tab.
  • the molding material mixtures were introduced into the molding tool from the storage bunker by means of 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 for the last 20 seconds.
  • the mold was opened and the test bar 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 led to the breakage of the test bars was measured.
  • the flexural strengths were determined according to the following scheme: 10 seconds after removal (hot strengths) approx. 1 hour after removal (cold strengths)
  • 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 made analogously to 1.1.1. manufactured. Their compositions are listed in Tab. 3. ⁇ b> Table ⁇ /b> 3 (Experiment 2) Composition of the molding material mixtures # Mold base material [GT] Binder [GT] amorphous SiO 2 [GT] Surfactant [GT] 2.1 100 a) 2.0 d) 0.5 f) not according to the invention 2.2 100 a) 2.0 e) 1.0 9) not according to the invention 2.3 100 a) 2.0 d) 0.5 h) according to the invention 2.4 100 b) 2.0 d) 0.5 f) not according to the invention 2.5 100 b) 2.0 d) 0.5 h) according to the invention 2.6 100 c) 2.0 d) 0.5 f) not according to the invention 2.7 100 c) 2.0 d) 0.5 h) according to the invention 2.8 100 a) 2.0 d) 0.5 f) 0.04 i) not according to the invention 2.9 100 a) 2.0 d) 0.5 h) 0.04
  • inlet channel cores which are larger and have a more complex geometry than the Georg Fischer bars ( Fig. 3 ).
  • the molding material mixtures were transferred to the storage bunker of a core shooter L 6.5 from Röperwerk-G manmaschinen GmbH, Viersen, DE, the molding tool of which was heated to 180 ° C., and from there they were introduced into the molding tool by means of compressed air.
  • the pressures used are listed in Tab. 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 for the last 20 seconds.
  • the mold was opened and the test bar removed.
  • Table 4 uses a core from foundry practice to confirm the improved flowability of the molding material mixtures according to the invention compared to the prior art.
  • the positive effect is independent of the type of sand and the shooting pressure.
  • Adding a surfactant in addition to the SiO 2 according to the invention brings about a further, albeit not as pronounced, improvement in the flowability as when using amorphous SiO 2 from other manufacturing processes.
  • the molding material mixtures were produced analogously to 1.1.1. Their compositions are given in Tab. 5. ⁇ b> Table ⁇ /b> 5 (Experiment 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) 0.025 g) not according to the invention 3.4 100 2.0 0.475 c) 0.025 h) not according to the invention 3.5 100 2.0 0.5 d) according to the invention 3.6 100 2.0 0.5 e) according to the invention 3.7 100 2.0 0.5 f) according to the invention a) Quarzwerke Frechen GmbH b) alkaline water glass; molar modulus approx.
  • the molding material mixture produced was transferred to the storage chamber of a core shooter H1 from Röperwerk-G manmaschinen GmbH, Viersen, DE. The remainder of the molding material mixture was kept in a carefully closed vessel until the core shooter was refilled to protect it from drying out and to avoid a premature reaction with the CO 2 present in the air.
  • the molding material mixtures were shot from the storage chamber by means of compressed air (4 bar) into a non-tempered molding tool provided with two engravings for round cores with a diameter of 50 mm and 50 mm in height.
  • CO 2 was first added for 6 seconds at a CO 2 flow of 2 L / min. and then passed through the molding tool filled with the molding material mixture for 45 seconds at a pressure of 4 bar. The temperatures of both gases were around 23 ° C when they entered the mold.
  • CO 2 was used at a CO 2 flow of 4 L / min. passed through the molding tool filled with the molding material mixture.
  • the temperature of the CO 2 when it entered the mold was approx. 23 °.
  • Tab. 7 shows the gas times with CO 2.
  • Table 6 ⁇ /b> (Experiment 3) Compressive strengths and core weights during curing with a combination of CO ⁇ sub> 2 ⁇ /sub> and air # Immediate strengths [N / cm 2 ] Strengths after 24 hours [N / cM 2 ] Core weight [g] 3.1 56 238 141.1 not according to the invention 3.2 173 289 143.3 not according to the invention 3.3 193 280 143.1 not according to the invention 3.4 189 300 143.4 not according to the invention 3.5 214 383 151.1 according to the invention 3.6 197 371 149.3 according to the invention 3.7 195 333 148.4 according to the invention # Immediate strengths [N / cm 2 ] Strengths after 24 hours a) [N / cm 2 ] Strengths after 4 days b) [N / cm 2 ] Strengths after 6 days b) [N / cm 2 ] 3.1 63 248 215 188 not according to the invention
  • Tab. 8 shows the aeration times with air.
  • Table ⁇ /b> 8 (Experiment 3) Compressive strengths when cured by CO ⁇ sub> 2 ⁇ /sub> # Aeration time [sec] Immediate strengths [N / cm 2 ] Strengths after 24 hours [N / cm 2 ] 10 12th 64 15th 20th 57 20th 24 51 3.1 30th 35 44 not according to the invention 45 40 46 60 42 45 90 43 38 10 33 67 15th 42 65 20th 46 66 3.2 30th 49 57 not according to the invention 45 51 54 60 56 52 90 57 48 10 40 93 15th 48 94 20th 48 95 3.5 30th 54 88 according to the invention 45 60 83 60 63 78 90 67 67 67
  • test bodies were removed from the mold and their compressive strengths were determined with a Zwick universal testing machine (model Z 010) immediately, ie a maximum of 15 seconds after removal.
  • compressive strengths of the test bodies were tested after 24 hours, in some cases also after 3 and 6 days of storage in a climatic cabinet. With the help of a climatic cabinet (Rubarth Apparate GmbH), constant storage conditions could be guaranteed.
  • 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 hardening by CO 2 and air. Weighing was carried out on a laboratory balance with an accuracy of 0.1 g.
  • Quartz sand from Quarzwerke Frechen GmbH was poured into the bowl of a mixer from Hobart (model HSM 10). While stirring, the hardener and then the binder were then added and mixed intensively with the sand for 1 minute.
  • composition of the molding material mixtures used to produce the test specimens is listed in Table 10 in parts by weight (GT).
  • the molding material mixture produced was introduced by hand into a molding tool with 8 engravings and compacted by pressing with a hand plate.
  • VZ The processing time (VZ), ie the time within which a molding material mixture can be compacted without any problems, was determined visually. You can tell that the processing time has been exceeded by the fact that a molding material mixture no longer flows freely, but rolls off like clods.
  • the processing times of the individual mixtures are given in Table 10.
  • AZ stripping time
  • a second part of the respective mixture was poured by hand into a round mold 100 mm high and 100 mm in diameter and also compacted with a hand plate.
  • the surface hardness of the compacted molding material mixture was then tested at certain time intervals with the Georg Fischer surface hardness tester. As soon as a molding material mixture is so hard that the test ball no longer penetrates the core surfaces, the stripping time has been reached.
  • the stripping times of 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 led to the breakage of the test bars was measured.
  • Table 11 shows the positive effects of the particulate amorphous SiO 2 used in terms of 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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  • Chemical & Material Sciences (AREA)
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  • Mold Materials And Core Materials (AREA)
EP13811773.4A 2012-10-19 2013-10-18 Formstoffmischungen auf der basis anorganischer bindemittel und verfahren zur herstellung von formen und kerne für den metallguss Active EP2908968B1 (de)

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EP21199894.3A EP3950168A1 (de) 2012-10-19 2013-10-18 Formstoffmischungen auf der basis anorganischer bindemittel zur herstellung von formen und kernen für den metallguss

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HUE058306T2 (hu) 2022-07-28
MX2015004904A (es) 2015-07-21
EP2908968A2 (de) 2015-08-26
CN104736270A (zh) 2015-06-24
CN104736270B (zh) 2018-10-09
US20150246387A1 (en) 2015-09-03
ES2906237T3 (es) 2022-04-13
RU2015118399A (ru) 2016-12-10
MX371009B (es) 2020-01-13
EP3950168A1 (de) 2022-02-09
JP2015532209A (ja) 2015-11-09
KR102104999B1 (ko) 2020-06-01
WO2014059967A2 (de) 2014-04-24
US10092946B2 (en) 2018-10-09
PL2908968T3 (pl) 2022-04-19
BR112015008549A2 (pt) 2017-07-04
JP6397415B2 (ja) 2018-09-26
DE102012020509A1 (de) 2014-06-12
KR20150074109A (ko) 2015-07-01
WO2014059967A3 (de) 2014-07-17
ZA201502169B (en) 2016-01-27
BR112015008549B1 (pt) 2019-11-19
RU2650219C2 (ru) 2018-04-11

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