EP2841220A1 - Procédé pour produire des moules et des noyaux pour la coulée de métaux ainsi que moules et noyaux produits au moyen de ce procédé - Google Patents

Procédé pour produire des moules et des noyaux pour la coulée de métaux ainsi que moules et noyaux produits au moyen de ce procédé

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Publication number
EP2841220A1
EP2841220A1 EP13726092.3A EP13726092A EP2841220A1 EP 2841220 A1 EP2841220 A1 EP 2841220A1 EP 13726092 A EP13726092 A EP 13726092A EP 2841220 A1 EP2841220 A1 EP 2841220A1
Authority
EP
European Patent Office
Prior art keywords
gas
molding material
mold
weight
binder
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.)
Withdrawn
Application number
EP13726092.3A
Other languages
German (de)
English (en)
Inventor
Diether Koch
Oliver Schmidt
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
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Filing date
Publication date
Application filed by ASK Chemicals GmbH filed Critical ASK Chemicals GmbH
Publication of EP2841220A1 publication Critical patent/EP2841220A1/fr
Withdrawn legal-status Critical Current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
    • 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
    • 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
    • B22C9/123—Gas-hardening

Definitions

  • the invention relates to a process for the production of molds and cores, wherein a molding material mixture of at least one refractory material and a CO2-curable binder, preferably containing or consisting of water glass, by gassing with CO 2 or a C0 2 -containing gas and rinsing with a second gas containing no CO 2 , but at least less CO 2 , is cured. Furthermore, the invention relates to the forms and cores produced by this process.
  • a refractory molding base e.g. Quartz sand
  • a suitable binder for the production of molds and cores i.A. a refractory molding base, e.g. Quartz sand, and a suitable binder.
  • the refractory molding base material is preferably present in a free-flowing form, so that the mixture of mold base material and binder, the so-called molding material mixture, filled into a suitable mold, can be compacted and cured there.
  • the binder produces a firm cohesion between the particles of the mold base, so that the molds and cores obtain the required mechanical stability.
  • Molds form the outer wall of the casting during casting, cores are used when cavities are required within the casting. It is not absolutely necessary that the forms and cores are made of the same material. Thus, e.g. In chill casting, the external shape of the castings with the help of metallic permanent molds. Also, a combination of shapes and cores produced by different methods is possible. What is explained below with reference to cores applies analogously to molds produced by the same process (casting molds) and vice versa.
  • the curing is usually carried out by a chemical reaction, which is triggered for example by the fact that a gas is passed through the molding mixture to be cured.
  • a chemical reaction which is triggered for example by the fact that a gas is passed through the molding mixture to be cured.
  • the molding material mixture is heated to a temperature sufficiently high after shaping by the heated mold to expel, for example, the solvent contained in the binder and / or to initiate a chemical reaction by which the binder is cured by, for example, crosslinking.
  • DE 10201 1010548-A1 describes a method for curing water-glass-bonded molding mixtures, wherein a combination of air and carbon dioxide flow is used. It turned out that the molding material mixture must first be perfused with air and then with CO2 or with an air-carbon dioxide mixture. Furthermore, it is of great importance for this invention that the alkali metal silicate solutions used have a weight ratio of SiO 2 to metal oxide in the range from 1.5: 1 to 2.0: 1. Another patent which describes such a method is WO 80/01254 A1. This discloses a method for curing a water glass-containing molding material mixture, which is heated at a temperature of 1 10 to 180 ° C and at the same time CO2 or a CO2-air mixture is passed.
  • the PL 129359 B2 describes a binder for the production of molds for metal casting, which is composed of water glass and urea resin. The curing takes place by flushing the molding material mixture with a CO 2 -air mixture. It is advantageous if the gases are heated to temperatures of 60-200 ° C.
  • Another publication describing the use of a CO 2 -air mixture is CN 941 1 1 187 A.
  • EP 2014392 B1 discloses the use of amorphous spherical SiO 2 , which is present in more than two particle size classifications.
  • EP 2014392 B1 does not disclose the use of a second gas stream and brings the SiO 2 in aqueous suspension, which is disadvantageous because of the increased water input for the (early) strengths of molded articles produced by the present inventive method. Good strength even after short curing times are necessary to be able to safely handle the ever more complicated thin-walled casting molds, which are increasingly required today, and at the same time to ensure high productivity. It is therefore not surprising that the water glass CO 2 process has rapidly lost importance with the advent of processes based on organic binders, in particular the so-called Ashland polyurethane cold box process.
  • the inventors have therefore set themselves the task of developing a process that allows molds and cores using a C0 2 -hardenable binder on an inorganic basis to produce in unheated tools, the strengths of the same binder and identical binder content Already without subsequent heat treatment should be much higher than in the previously known cure with CO 2 , especially immediately after removal from the mold.
  • first gas and second gas should not be interpreted as giving up the first gas before the second gas, on the contrary, the sequences can be any and also first and / or second gas can also be given up several times. However, it is preferred that the second gas be last and independently of this, the first gas first introduced into the mold.
  • gas temperatures in the fumigation between 15 ° C and 120 ° C, preferably 15 ° C and 100 ° C, and particularly preferably between 25 ° C and 80 ° C, are advantageous.
  • the gas temperature refers here as well as in the further description of the method according to the invention to the temperature which has the gas entering the mold.
  • the second gas also preferably has gas temperatures of 15 to 120 ° C, preferably between 15 ° C to 100 ° C, and more preferably between 25 ° C and 80 ° C, however, higher temperatures often allow shortening of the purge time. An upper limit due to the curing mechanism does not exist.
  • the temperatures will be between 40 ° C and 250 ° C, preferably between 50 ° C and 200 ° C. Economic reasons speak against the use of very high temperatures, since the prices of the heaters required for this increase sharply with increasing power and the cost for effective insulation of the lines is very high.
  • the temperature of the first gas is about the same as the temperature of the second gas.
  • the temperature of the second gas is higher than the temperature of the first gas.
  • the use of existing heatable molds is by no means excluded in the described method, it opens up the possibility of the tools for cost reduction either cold, ie at ambient or room temperature of 15 to 30 ° C, or at lower than that operate at normal temperatures, ie lower than 200 ° C, or lower than 120 ° C or even lower than 100 ° C, in particular cheaper non-heated tools can be used.
  • Such tools are not heatable, ie they have no heating device itself such as an electric heater, but can be heated by the introduced tempered gas.
  • the inventive method also does not exclude, then subject the cores or molds to an additional heat treatment.
  • the method according to the invention comprises the steps:
  • the procedure is such that the refractory molding base material is initially charged and the binder is added with stirring. It is stirred further until a uniform distribution of the binder is ensured on the molding material.
  • the molding material mixture is then brought into the desired shape.
  • customary methods are used for the shaping.
  • the molding material mixture can be shot by means of a core shooting machine with the aid of compressed air into the mold. Curing then takes place by first passing (in particular) the CO 2 gas through the tool filled with the molding material mixture, followed by a post-rinse with the second gas. It is immediately clear to the person skilled in the art that there are various design possibilities for this process.
  • the CO 2 - gas contains at least 50% by volume C0 2, preferably at least 80% by volume of C0. 2
  • the second gas it is not necessary for the second gas to be completely CO 2 -free, such as synthetic air or nitrogen.
  • air is preferred.
  • the purge gas may even be mixed with CO 2 , but not more than 10% by volume, more preferably not more than 5% by volume, in particular not more than 2% by volume or even not more than 1% by volume.
  • the transition from C0 2 gas to the second gas need not be done in one step, gradual or fluid transitions are also possible.
  • both gases or just one of them can be pulsed through the molding material mixture.
  • a further variant consists of first removing a portion of the water present in the molding material mixture by a short gassing with the C0 2 -pure gas as purge gas, then curing the binder with the C0 2 gas and optionally again the core for further drying to treat with the C0 2 low-gas.
  • the dosage of CO 2 can be done either by setting a specific C0 2 flow for the C0 2 gas or a certain gassing pressure. For which of the two options one chooses in practice, depends on many factors, such as the geometry and size of the core, the tightness of the mold, the ratio of gas inlet to gas outlet, the gas permeability of the molding material, the diameter of the Gas line, binder content, desired gassing time, etc. To optimize the properties, the gassing parameters may be adjusted depending on the requirements of the selected core or mold geometry within the scope of the present disclosure and those of ordinary skill in the art. As a rule, a CO 2 -FIUSS between 0.5 L / min. and 600 L / min. choose, preferably between 0.5 L / min.
  • the CO 2 -FIUSS is between 0.5 L / min. and 30 L / min. choose, preferably between 0.5 L / min. and 25 L / min. and more preferably between 0.5 L / min. and 20 L / min.
  • This embodiment is particularly advantageous at low gas temperatures for the CO 2 or the CO 2 -containing gas of 15 to 40 ° C.
  • the pressures of the CO 2 gas usually move between 0.5 bar and 10 bar, preferably between 0.5 bar and 8 bar and more preferably between 0.5 bar and 6 bar.
  • air as a purge gas, this can be taken from the compressed air network usually found in foundries, so that the pressure prevailing therein represents the upper limit for gassing for purely practical reasons.
  • the lower limit for effective fumigation with air is about 0.5 bar. At a lower pressure, the fumigation time would be greatly prolonged, which would be associated with a loss of productivity.
  • the ratio of the gassing of the first (CO 2 gas) and second gas (purge gas) to one another for example between 2:98 to 90:10, preferably between 2:98 to 20:80 and particularly preferably between 5:95 to 30: 70 vary.
  • the fumigation time with the CO 2 gas should preferably not exceed 60% of the total gasification time, particularly preferably not more than 50%.
  • a refractory molding base material can be used for the production of molds usual materials. Suitable examples are quartz, zircon or chrome ore sand, olivine, vermiculite, bauxite and chamotte. It is not necessary to use only new sands. In terms of resource conservation and to avoid landfill costs, it is even advantageous to use the highest possible proportion of regenerated used sand.
  • regenerates which are obtained by washing and subsequent drying. Applicable but less preferred are regenerates obtained by purely mechanical treatment. As a rule, the regenerates can replace at least about 70% by weight of the new sand, preferably at least about 80% by weight and more preferably at least about 90% by weight.
  • refractory mold raw materials and artificial molding materials may be used such.
  • Glass beads, glass granules the known under the name “Cerabeads” or “Carboaccucast” spherical ceramic mold base materials or Aluminiumiumsilikatmikrohohlkugeln (so-called Microspheres).
  • Such aluminosilicate hollow microspheres are marketed, for example, by Omega Minerals Germany GmbH, Norderstedt, in various qualities with different contents of aluminum oxide under the name “Omega-Spheres.”
  • Corresponding products are available from PQ Corporation (USA) under the name “Extendospheres”. available.
  • the average diameter of the molding base materials is generally between 100 and 600 ⁇ m, preferably between 120 ⁇ m and 550 ⁇ m, and particularly preferably between 150 ⁇ m and 500 ⁇ m. determined by sieving according to DIN ISO 3310.
  • the preferred proportion of the artificial molding base materials is at least about 3% by weight, particularly preferably at least 5% by weight, particularly preferably at least 10% by weight, preferably at least about 15% by weight, particularly preferably at least about 20% by weight. , based on the total amount of refractory molding material.
  • the refractory molding base material preferably has a free-flowing state, so that the molding material mixture according to the invention can be processed in conventional core shooting machines.
  • the molding material mixture according to the invention comprises a water glass-based binder.
  • a water glass while standard water glasses can be used, as they are already used as binders in molding material mixtures.
  • Water glasses are aqueous solutions of alkali silicates, especially lithium, sodium and potassium silicates and are also found in other fields such as e.g. in construction application as a binder.
  • alkali silicates especially lithium, sodium and potassium silicates
  • the glass of water is initially in the form of a piece of solid glass, which is dissolved in water using temperature and pressure.
  • Another method for the production of water glasses is the direct dissolution of quartz sand with caustic soda.
  • the alkali silicate solution obtained can then be adjusted to the desired molar ratio SiO 2 / M 2 O by addition of alkali hydroxides and / or alkali oxides and their hydrates. Furthermore, the composition of the alkali silicate solution can be adjusted by dissolving alkali silicates having a different composition.
  • hydrous alkali metal silicates present in solid form such as, for example, the product groups Kasolv, Britesil or Pyramid from PQ Corporation, are also suitable.
  • the water glass preferably has a molar modulus S1O2 / M2O in the range from 1.6 to 4.0, in particular 2.0 to less than 3.5, where M is lithium, sodium or potassium.
  • the water glasses preferably have a solids content greater than or equal to 30% by weight, more preferably greater than or equal to 33% by weight, and particularly preferably greater than or equal to 36% by weight.
  • the upper limits for the solids content of the preferred water glasses are less than or equal to 65% by weight, more preferably less than or equal to 60% by weight and particularly preferably less than or equal to 55% by weight.
  • the water glasses have a solids content, calculated as M 2 O and S1O 2, in the range from 25 to 65% by weight, preferably from 30 to 60% by weight.
  • the solids content refers to the amount of alkali silicates contained in the water glass, calculated as S1O2 and M2O.
  • the water glass-based binder preferably between 0.5% by weight and 5% by weight of the water glass-based binder are used, preferably between 0.75% by weight and 4% by weight, particularly preferably between 1% by weight and 3, 5 wt.%, Each based on the molding material.
  • the term refers to water glasses with a solids content as indicated above and includes the diluent water.
  • the amount of binder used is 0.2 to 2.5% by weight. , preferably 0.3 to 2 wt.% Relative to the molding material, wherein M 2 0 has the meaning given above.
  • the molding material mixture further contains a proportion of a particulate metal oxide which is selected from the group of silica, alumina, titania and zinc oxide and mixtures thereof or mixed oxides, in particular silica, alumina and / or aluminosilicates.
  • the particle size of these metal oxides is preferably less than 300 ⁇ , preferably less than 200 ⁇ , more preferably less than 100 ⁇ and has, for example, an average primary particle size between 0.05 ⁇ and 10 ⁇ .
  • the particle size can be determined by sieve analysis. More preferably, the sieve residue on a sieve with a mesh size of 63 ⁇ less than 10 wt .-%, preferably less than 8 wt .-%. Particularly preferred as the particulate metal oxide silica is used, in which case synthetically produced amorphous silica is particularly preferred. As the particulate silica, precipitated silica and / or fumed silica is preferably used.
  • the amorphous SiO 2 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 amorphous S1O2 is used as a powder.
  • amorphous S1O2 both synthetically produced and naturally occurring silicas can be used. However, the latter, known for example from DE 102007045649, are not preferred because they usually contain not inconsiderable crystalline fractions and are therefore classified as carcinogenic.
  • Synthetically, non-naturally occurring amorphous S1O2 is understood, ie the production thereof comprises a chemical reaction, for example the preparation of silica sols by ion exchange processes from alkali silicate solutions, the precipitation from alkali silicate solutions, the flame hydrolysis of silicon tetrachloride or the reduction of quartz sand with coke in the electric arc furnace during the production of Ferrosilicon and silicon.
  • the amorphous SiO 2 produced by the latter two processes is also referred to as pyrogenic SiO 2 .
  • synthetic amorphous S1O2 is understood as meaning only precipitated silica (CAS No. 1 12926-00-8) and SiO 2 produced by flame hydrolysis (Pyrogenic Silica, Fumed Silica, CAS No. 1 12945-52-5), while in the case of ferrosilicon or silicon-produced product only as amorphous Si0 2 (Silica Fume, Microsilica, CAS No. 69012-64-12) is called.
  • the product formed in the production of ferrosilicon or silicon is also understood as a synthetic amorphous S1O2.
  • quartz glass powder mainly amorphous SiO 2 which has been produced by melting and rapid re-cooling of crystalline quartz, so that the particles are spherical and not splintered (see DE 10201202051 1).
  • the average primary particle size of the synthetic amorphous silicon dioxide can be between 0.05 ⁇ m and 10 ⁇ m, in particular between 0.1 ⁇ m and 5 ⁇ m, more preferably between 0.1 ⁇ m and 2 ⁇ m.
  • the primary particle size was determined by means of dynamic light scattering on a Horiba LA 950 and checked by scanning electron micrographs (SEM images) on a Nova NanoSEM 230 from FEI. Furthermore, details of the primary particle shape up to the order of 0.01 ⁇ could be made visible with the aid of SEM images.
  • the SiO2 samples were dispersed in distilled water for SEM measurements and then coated on a copper banded aluminum holder before the water was evaporated.
  • the specific surface area of the synthetic amorphous silicon dioxide was determined by means of gas adsorption measurements (BET method) according to DIN 66131.
  • the specific surface area of the synthetic amorphous SiO 2 is between 1 and 200 m 2 / g, in particular between 1 and 50 m 2 / g, more preferably between 1 and 30 m 2 / g. If necessary.
  • the products can also be mixed, for example to obtain specific mixtures with certain particle size distributions.
  • the amorphous SiO 2 types mentioned form slightly larger aggregates.
  • the aggregates partially break up again during mixing in smaller units or not exceed a certain size from the outset.
  • the residue when passing through a 45 mesh sieve (325 mesh) is not more than about 10 weight percent, more preferably not more than about 5 weight percent. and most preferably not more than about 2% by weight.
  • the purity of the amorphous SiO 2 can vary greatly. Types having a content of at least 85% by weight of SiO 2 , preferably of at least 90% by weight and more preferably of 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, more preferably between 0.1% % By weight and 1.5% by weight, based in each case on the basic molding material.
  • the ratio of water glass binder to amorphous SiO 2 can be varied within wide limits. This offers the advantage of greatly improving the initial strengths of the cores, ie, the strength immediately after removal from the tool, without significantly affecting the ultimate strengths. This is of great interest especially in light metal casting. On the one hand, high initial strengths are desired in order to be able to easily transport the cores after their production or to assemble them into whole core packages, on the other hand, the final strengths should not be too high to avoid difficulties in core decay after casting.
  • the amorphous SiO 2 is preferably present in a proportion of from 2 to 60% by weight, more preferably from 3 to 55% by weight, and especially preferably from 4 to 50% by weight or particularly preferably based on the ratio Solids content of water glass to amorphous Si0 2 from 10: 1 to 1: 1, 2 (parts by weight).
  • the strongly alkaline water glass can react with the silanol groups located on the surface of the amorphous silica and that upon evaporation of the water, an intense bond between the silica and the then solid water glass is produced ,
  • barium sulfate may be added to the molding material mixture in order to further improve the surface of the casting, in particular in light metal casting, such as aluminum casting.
  • the barium sulfate may be synthetically produced as well as natural barium sulfate, i. be added in the form of minerals containing barium sulfate, such as barite or barite. This and other features of the suitable barium sulfate and of the molding material mixture produced therewith are described in more detail in DE 102012104934 and the disclosure content thereof is also made by reference to the disclosure of the present patent.
  • the barium sulfate is preferably used in an amount of 0.02 to 5.0% by weight, more preferably 0.05 to 3.0% by weight, particularly preferably 0.1 to 2.0% by weight, or 0.3 to 0 , 99% by weight, in each case based on the entire molding material mixture added.
  • other substances which are distinguished by a low wetting with molten aluminum for example boron nitride, can also be added to the molding material mixture according to the invention.
  • Such a mixture of low-wetting substances which contains, inter alia, barium sulfate as a low-wetting agent, can likewise lead to a smooth, sand-bond-free casting surface.
  • the proportion of barium sulfate should be greater than 5% by weight, preferably greater than 10% by weight, particularly preferably greater than 20% by weight or greater than 60% by weight.
  • the upper limit is pure barium sulfate - the proportion of barium sulfate in non-wetting agents in this case is 100% by weight.
  • the mixture of non-wetting / low-wetting substances, in particular barium sulfate, is preferably used in an amount of 0.02 to 5.0% by weight, more preferably 0.05 to 3.0% by weight, particularly preferably 0.1 to 2.0 % By weight or 0.3 to 0.99% by weight, based in each case on the molding material mixture.
  • the additive component of the molding material mixture according to the invention may further comprise at least one particulate or a particulate mixed metal oxide of aluminum or of aluminum and zirconium, as described in DE 1020121 13073 and DE 1020121 13074, respectively .
  • the particulate or mixed metal oxide shows no or at least a very low reactivity with the inorganic binder, in particular the alkaline water glass, at room temperature.
  • the particulate metal oxide comprises or consists in particular of at least one aluminum oxide in the alpha phase and / or at least one aluminum / silicon mixed oxide, with the exception of aluminum / silicon mixed oxides having a phyllosilicate structure.
  • Particulate metal oxides containing at least one alpha-phase aluminum oxide and / or at least one aluminum / silicon mixed oxide are understood to be not only particulate metal oxides which are pure alumina or pure aluminosilicates or aluminosilicates exist but also mixtures of the above metal oxides with other oxides such as zirconium, zirconium incorporated into the aluminum / silicon mixed oxides or heterogeneous, ie consisting of several phases mixtures which consist inter alia of at least two of the following solids or phases: alumina-containing and / or aluminum / silicon oxide-containing solids or phases.
  • particulate metal oxide selected from the group of corundum plus zirconium dioxide, zirconium mullite, zirconium corundum and aluminum silicates (with the exception of those having a layered silicate structure) plus zirconium dioxide and, if appropriate, optionally containing further metal oxides.
  • the particulate mixed metal oxide is at least one particulate compound oxide or particulate mixture of at least two oxides or is present at least as a particulate composite oxide adjacent at least one further particulate oxide, wherein the particulate mixed metal oxide comprises at least one oxide of aluminum and at least one oxide of zirconium.
  • particulate mixed metal oxides containing in addition to an oxide of aluminum additionally an oxide of zirconium are understood not only pure aluminum oxides and zirconium oxides, but also mixed oxides such as aluminum silicates and zirconium oxide or heterogeneous, ie consisting of several phases mixtures of substances including a or several alumina-containing and zirconium oxide-containing solids or phases.
  • the particulate mixed metal oxide according to the invention is selected from one or more members of the group of a) corundum plus zirconium dioxide, b) zirconium mullite, c) zirconium corundum and d) aluminum silicates plus zirconium dioxide and can optionally additionally contain further metal oxides.
  • Aluminum silicates are here understood as meaning both aluminosilicates and aluminosilicates. Both the aluminum / silicon mixed oxides and the aluminum silicates, if they are not amorphous (ie, there is crystallinity or partial crystallinity here), are preferably island silicates. In isolated silicates, the Si0 4 units (tetrahedral) contained in the structure are not directly linked to each other (no Si-O-Si linkages), instead, there are links of the tetrahedral Si0 4 units to one or more Al atoms (Si-O Al). The Al atoms are coordinated by 4, 5, and / or 6 oxygen atoms.
  • Typical representatives of these island silicates are (according to the classification of minerals according to Strunz, 9th edition), for example, mullite (melt and sintered mullite are meant here as well as Zr0 2 -containing mullite) and sillimanite and other members of the sillimanite group (for example kyanite or andalusite ), wherein from the sillimanite group particularly preferably kyanite is used.
  • an amorphous aluminum silicate (except those with phyllosilicate structure) with greater than 50 atomic% of aluminum atoms based on the sum of all silicon and aluminum atoms, possibly also containing zirconium / zirconium oxide, or an alumina-containing dust, which as by-product produced in zirconium corundum production and therefore may contain zirconium oxide in finely divided form.
  • zirconium / zirconium oxide possibly also containing zirconium / zirconium oxide, or an alumina-containing dust, which as by-product produced in zirconium corundum production and therefore may contain zirconium oxide in finely divided form.
  • the particulate amorphous silica added to the molding compound mixture to increase the strengths may be added as part of the particulate mixed metal oxide or separately.
  • the statements made herein on the concentration of the particulate mixed metal oxide and the particulate amorphous silica are each without the other component (s). In case of doubt the component has to be calculated out.
  • the additive component of the molding material mixture according to the invention may comprise a phosphorus-containing compound.
  • a phosphorus-containing compound such an addition is preferred in very thin-walled sections of a casting mold and in particular in cores, since in this way the thermal stability of the cores or of the thin-walled section of the casting mold can be increased. This is of particular importance when the liquid metal encounters an inclined surface during casting and exerts a strong erosive effect there due to the high metallostatic pressure or can lead to deformations of thin-walled sections of the casting mold in particular. Suitable phosphorus compounds do not or not significantly affect the processing time of the novel molding material mixtures. Suitable representatives and their added amounts are described in detail in WO 2008/046653 A1 and this is also claimed to the extent of the disclosure of the present patent.
  • the molding material mixture according to the invention contains a proportion of platelet-shaped lubricants, in particular graphite or M0S2.
  • platelet-shaped lubricants in particular graphite or M0S2.
  • the amount of added platelet-shaped lubricant, in particular graphite, is preferably 0.05 wt.% To 1 wt.%, Based on the molding material.
  • the molding material mixture according to the invention may also comprise further additives.
  • internal release agents can be added which facilitate the detachment of the molds from the mold. Suitable internal release agents are e.g. Calcium stearate, fatty acid esters, waxes, natural resins or special alkyd resins.
  • 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 novolacs, polyols, such as polyethylene glycols or polypropylene glycols, glycerol or polyglycerol, polyolefins, such as Polyethylene or polypropylene, copolymers of olefins, such as ethylene or propylene, and further comonomers, such as vinyl acetate or styrene and / or diene monomers, Polyamides such as polyamide-6, polyamide-12 or polyamide-6,6, natural resins such as gum rosin, fatty acid esters such as cetyl palmitate, fatty acid amides such as ethylenediamine bisstearamide, carbohydrates such as dextrins and metal soaps such
  • the organic additives are preferably in an amount of 0.01 to 1 wt.%, Or 0, 1 -1, 0 wt.%, Particularly preferably 0.05 to 0.5 wt.%, Particularly preferably 0, 1 -0 , 2% by weight, in each case based on the molding material added.
  • silanes can also be added to the molding material mixture according to the invention in order to increase the resistance of the molds and cores to high air humidity and / or water-based molding coatings.
  • the molding material mixture according to the invention contains a proportion of at least one silane.
  • Suitable silanes are, for example, aminosilanes, epoxysilanes, mercaptosilanes, hydroxysilanes and ureidosilanes.
  • suitable silanes are ⁇ -aminopropyltrimethoxysilane, ⁇ -hydroxypropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, ⁇ -
  • alkali metal siliconates for example potassium methyl siliconate, of which 0.5 to 15% by weight, preferably 1 to 10% by weight and more preferably 1 to 5% by weight, based on the binder, can be used.
  • the molding material mixture comprises an organic additive, then it can be added per se at any point in time during the preparation of the molding material mixture.
  • the addition of the organic additive can be carried out 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 over several months in the binder, they can also be dissolved in the binder and thus added together with this the molding material.
  • Water-insoluble additives may be used in the form of a dispersion or a paste.
  • the dispersions or pastes preferably contain water as the liquid medium.
  • Inorganic additives can also positively influence the properties of the cores produced by the process according to the invention.
  • the refractory molding base material is placed in a mixer and then preferably first added the liquid component and mixed with the refractory molding material until a uniform layer of the binder has formed on the grains of the refractory molding material.
  • the mixing time is chosen so that an intimate mixing of refractory base molding material and liquid component takes place.
  • the mixing time depends on the quantity of the molding material mixture to be produced and on the mixing unit used. Preferably, the mixing time is selected between 1 and 5 minutes.
  • the solid component (s) in the form of the particulate mixed metal oxides, and optionally of the amorphous silicon dioxide, barium sulfate or other powdered solids is then added and then the mixture further mixed.
  • the mixing time depends on the amount of the molding mixture to be produced and on the mixing unit used. Preferably, the mixing time is selected between 1 and 5 minutes.
  • a liquid component is understood to mean both a mixture of different liquid components and the totality of all liquid individual components, the latter being able to be added to the molding material mixture together or else successively.
  • the solid components may first be added to the refractory base molding material and only then the liquid component of the mixture to be supplied. The molding material mixture is then brought into the desired shape. In this case, customary methods are used for the shaping. For example, the molding material mixture can be shot by means of a core shooting machine with the aid of compressed air into the mold.
  • Another possibility is to trickle the molding material mixture free-flowing from the mixer into the mold and to compact them there by shaking, stamping or pressing.
  • the processes according to the invention are in themselves suitable for the production of all casting molds customary for metal casting, that is to say, for example, of cores and molds.
  • the cores produced with the molding material mixture according to the invention show a good disintegration after the casting, in particular during aluminum casting.
  • the use of the moldings produced from the molding material mixture according to the invention is not limited to light metal casting.
  • the molds are generally suitable for casting metals.
  • Such metals include, for example, non-ferrous metals, such as brass or bronze, and ferrous metals.
  • a portion of the molding material mixtures prepared according to 1 .1 or 1 .2 were transferred to the storage chamber of a core shooter H 1 Fa. Röperwerke AG. The remainder of the molding mixtures were stored in a carefully sealed vessel until replenishment of the core shooter to prevent dehydration and premature reaction with the CO2 present in the air. From the storage chamber, the molding material mixtures were shot by means of compressed air (4 bar) into a non-tempered mold provided with two engravings for round cores of 50 mm diameter and 50 mm height. Subsequently, the test cores were cured. Details about it are listed in the respective experiments.
  • test specimens were removed from the mold and their compressive strengths were determined immediately using a Zwick Universal Testing Machine (Model Z 010), ie a maximum of 15 seconds after removal, and after storage for 24 hours.
  • the values listed in the tables are averages of 8 cores each.
  • all test specimens used to determine the 24 hourly strengths were stored in a climatic chamber at 23 ° C and 50% humidity.
  • the experiments were carried out on a core shooter L 1 from. Laempe & Mössner GmbH, which was equipped with a heating hose (type HT42-13) from. Hillesheim GmbH.
  • GT parts by weight
  • CO2 manufactured and purity in each case: Linde AG, at least 99.5 vol.% CO2.
  • the temperature of the gas was between 22 and 25 ° C when it entered the mold.
  • Table 1 lists the gassing times, the C0 2 flow and the compressive strengths found under these conditions (see Examples 1 .01 to 1 .21 and 1 .29 to 1 .42).
  • the strengths are dependent on the quantity of CU2 used for curing, the initial strengths increasing with increasing amount of CO2, the strengths falling after 24 hours of storage due to the known Matterbegasungs bines contrast (see Examples 1 .01 to 1 .21), the Sprintbegasungs bin expected to occur later at higher binder levels.
  • amorphous S1O2 causes an increase in strength over cores cured with the same fumigation parameters but not containing amorphous S1O2 (see Examples 1 .22 - 1 .28 compared to 1 .08 - 1 .14).
  • amorphous S1O2 causes a greater increase in the initial strengths than the increase in binder content by the same amount.
  • the ultimate strengths increase much more when the binder content is high, but they also decrease more strongly with long fumigation times because of the overgassing effect (see Examples 1 .22 - 1 .28 in comparison to 1 .29 - 1 .35).
  • the mixture of water glass binder and amorphous S1O2 offers advantages in terms of initial strengths compared to the increased binder quantity without amorphous S1O2, except for long gassing times.
  • the increased binder content has a stronger effect on the final strengths, with the decrease in strength again being pronounced for long fumigation times as a result of overgassing (see Examples 1 .22 - 1 .28 in comparison to 1 .36 - 1 .42). 4. curing with air
  • the strengths depend on the amount of air passed through, with the initial strengths increasing more with increasing air volume than the final strengths (see Examples 2.01 - 2.03 and 2.07 - 2.12).
  • a higher binder content does not necessarily result in better strengths. This can probably be explained by the poorer compressibility and the increased water content in the molding compound mixture (see examples 2.01 - 2.03 compared to 2.07 - 2.12).
  • amorphous SiO 2 provides an increase in strength over cores cured with the same fumigation parameters but containing no amorphous SiO 2 , with the initial strengths being more affected than the final strengths (see Examples 2.04 - 2.06 compared to 2.01 - 2.03).
  • the increase in strength by the amorphous SiO 2 is greater than by an increase in the binder content by the same amount (see Examples 2.07 - 2.09 compared to 2.04 - 2.06).
  • the increase in strength through the amorphous SiO 2 is greater than when the binder content is increased to the same solids content (see Examples 2.10 - 2.12 compared to 2.04 - 2.06). 5. Curing by a combination of CO2 and air
  • molding material mixtures consisting of quartz sand H 32 and 2.0 GT, 2.5 GT and 3.25 GT of a water glass with a molar modulus of about 2.33 and a solids content of about 40% by weight were used .
  • Table 3 shows the gassing times of C0 2 and air, the C0 2 flow, the gas pressure (air) and the compressive strengths found under these conditions (see Examples 3.01 - 3.09, 3.19 - 3.27, 3.37 - 3.45).
  • a higher binder content causes higher final strengths but not necessarily higher initial strengths. The latter can probably be explained by the increased proportion of water in the molding material mixture (see Examples 3.37-3.42 in comparison to 3.04-3.06)
  • amorphous S1O2 causes an increase in strength over cores cured with the same parameters but not containing amorphous S1O2, with the initial strengths being more affected than the final strengths.
  • the final strengths of some of the longer C02 gassing times are partially reduced (see examples 3.10-3.18 compared to 3.01 -3.09 and examples 3.28-3.36 compared to 3.19-3.27).
  • amorphous S1O2 causes a greater increase in initial strengths than the same amount of binder content.
  • the increased binder content has a stronger effect on the final strengths (see Examples 3.13-3.15 compared to 3.37-3.39)
  • the mixture of waterglass binder and amorphous S1O2 offers advantages in the initial strengths compared to the correspondingly increased binder quantity without amorphous S1O2.
  • the higher binder content has a stronger effect on the ultimate strengths (see Examples 3.13-3.15 compared to 3.40-3.42)
  • An increase in the pressure during the fumigation with air causes a further increase in strength (see Examples 3.46-3.48 compared to 3.13-3.15) 6.
  • molding material mixtures consisting of quartz sand H 32 and 2.0 GT of a water glass with a molar modulus of about 2.33 and a solids content of about 40% by weight were used. Furthermore, 0.5 g of amorphous silica in powder form was admixed with the molding material mixtures before the binder addition. For curing C0 2 and then compressed air was passed through the molding material mixture. Both gases were heated by means of a heating hose to temperatures of up to 120 ° C. The temperatures of both gases when entering the mold were initially 15 ° C and many at 90 ° C during the 35 second fumigation. This temperature drop is due to the fact that the heating hose is unable to keep the gas temperature constant during the gassing. Immediately prior to the start of the experiment, the 4.04 test was repeated approximately 80 times over a period of 50 minutes, so that the mold reached the required operating temperature of about 60 ° C.
  • Table 4 shows the gassing times of C0 2 and air, the C0 2 flow, the gas pressure (air) and the flexural strengths found under these conditions (see Examples 4.01 - 3.07).
  • Examples 4.01 -4.03, in which the curing was carried out exclusively with C0 2 have compared to Examples 4.05-4.07 of the process according to the invention significantly lower initial and, apart from Example 4.01, also final strengths.
  • the strengths of Example 4.04, which shows the values for air alone fumigation, are also significantly lower than the strengths for the combined C02 air fumigation according to the invention. While the final strengths for Examples 4.05-4.07 are 10-60 N / cm 2 above the values for Example 4.04, their initial strengths are 50-60 N / cm 2 higher.
  • the significantly higher initial strengths of Examples 4.05 to 4.07 make the effect according to the invention clear even at the here increased gas temperature of 15 to 90 ° C for the C0 2 and the air.
  • Examples 4.05 to 4.07 show only minor differences, but these are not significant.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mold Materials And Core Materials (AREA)
  • Molds, Cores, And Manufacturing Methods Thereof (AREA)

Abstract

L'invention concerne un procédé pour produire des moules de coulée et des noyaux, selon lequel un matériau de base de moule constitué d'au moins une matière réfractaire et d'un liant durcissable avec du CO2, de préférence à base de verre soluble, est durci par exposition à un gaz de type CO2 et lavé au moyen d'un deuxième gaz. Cette invention se rapporte en outre à des moules et à des noyaux produits au moyen du ce procédé.
EP13726092.3A 2012-04-26 2013-04-26 Procédé pour produire des moules et des noyaux pour la coulée de métaux ainsi que moules et noyaux produits au moyen de ce procédé Withdrawn EP2841220A1 (fr)

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DE102012103705A DE102012103705A1 (de) 2012-04-26 2012-04-26 Verfahren zur Herstellung von Formen und Kernen für den Metallguss sowie nach diesem Verfahren hergestellte Formen und Kerne
PCT/DE2013/000223 WO2013159762A1 (fr) 2012-04-26 2013-04-26 Procédé pour produire des moules et des noyaux pour la coulée de métaux ainsi que moules et noyaux produits au moyen de ce procédé

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CN (1) CN104470652A (fr)
BR (1) BR112014026456A2 (fr)
CA (1) CA2870115A1 (fr)
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US20150129155A1 (en) 2015-05-14
WO2013159762A1 (fr) 2013-10-31
JP2015514591A (ja) 2015-05-21
RU2014146801A (ru) 2016-06-20
DE102012103705A1 (de) 2013-10-31
KR20150006024A (ko) 2015-01-15
BR112014026456A2 (pt) 2017-06-27
CA2870115A1 (fr) 2013-10-31
CN104470652A (zh) 2015-03-25

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