EP2763807B1 - Beschichtungsmassen für anorganische giessformen und kerne enthaltend salze und deren verwendung - Google Patents

Beschichtungsmassen für anorganische giessformen und kerne enthaltend salze und deren verwendung Download PDF

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Publication number
EP2763807B1
EP2763807B1 EP12780402.9A EP12780402A EP2763807B1 EP 2763807 B1 EP2763807 B1 EP 2763807B1 EP 12780402 A EP12780402 A EP 12780402A EP 2763807 B1 EP2763807 B1 EP 2763807B1
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EP
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Prior art keywords
weight
sizing composition
casting mould
sizing
salts
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EP12780402.9A
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German (de)
English (en)
French (fr)
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EP2763807A2 (de
Inventor
Michael Kloskowski
Peter WACHTARCZYK
Carolin WALLENHORST
Stefan BEZOLD
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ASK Chemicals GmbH
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ASK Chemicals GmbH
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C3/00—Selection of compositions for coating the surfaces of moulds, cores, or patterns
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C9/00—Moulds or cores; Moulding processes
    • B22C9/02—Sand moulds or like moulds for shaped castings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C9/00—Moulds or cores; Moulding processes
    • B22C9/10—Cores; Manufacture or installation of cores
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C9/00—Moulds or cores; Moulding processes
    • B22C9/12—Treating moulds or cores, e.g. drying, hardening

Definitions

  • the invention relates to slip molds having a sizing composition as a coating composition. the production of such molds and the use of the size compositions.
  • the sizing composition is suitable for cores and molds made using waterglass as a binder under thermal cure.
  • the sizing composition contains certain salts.
  • Molds are available from a refractory material, such as quartz sand, to form into a casting mold and set by a suitable binder to ensure sufficient mechanical strength of the mold.
  • a refractory molding material such as quartz sand
  • a suitable binder for the production of molds is thus used a refractory molding material and a suitable binder.
  • the refractory molding base material is preferably present in a free-flowing form, so that it can be filled into a suitable mold and compacted there.
  • the binder produces a firm cohesion between the particles of the molding base material, so that the casting mold obtains the required mechanical stability.
  • both organic and inorganic binders can be used, the curing of which can be carried out in each case by cold or hot processes.
  • Cold processes are processes which are carried out essentially at room temperature without heating the casting mold.
  • the curing is usually carried out by a chemical reaction, which is triggered for example by the fact that a gas is passed as a catalyst through the mold to be cured.
  • hot processes the molding material mixture is heated to a sufficiently high temperature after molding to expel, for example, the solvent contained in the binder or to initiate a chemical reaction by which the binder is cured, for example, by crosslinking.
  • binder systems which are based on inorganic materials or contain a very low proportion of organic compounds. Such binder systems have been known for some time.
  • Binder systems have been developed which can be cured by the introduction of gases. Such a system is for example in the GB 782205 described in which an alkali water glass is used as a binder, which can be cured by the introduction of CO 2 .
  • an exothermic feeder composition containing an alkali metal silicate as a binder In the US 6972059 B1 describes an exothermic feeder composition containing an alkali metal silicate as a binder.
  • binder systems have been developed which are self-curing at room temperature. Such, based on phosphoric acid and metal oxides system is eg in the US 5582232A described.
  • inorganic binder systems are known which are cured at higher temperatures, for example in a hot tool.
  • Such thermosetting binder systems are for example from US 5474606 A in which a binder system consisting of alkali water glass and aluminum silicate is described.
  • the waterglass-based binder system consists of an aqueous alkali silicate solution and a hygroscopic base, such as sodium hydroxide, added in a ratio of 1: 4 to 1: 6.
  • the water glass has a modulus SiO 2 / M 2 O of 2.5 to 3.5 and a solids content of 20 to 40%.
  • the binder system still contains a surface-active substance, such as silicone oil, which has a boiling point ⁇ 250 ° C.
  • the binder system is mixed with a suitable refractory material, such as quartz sand, and then injected into a core box with a core shooter.
  • metal salts such as magnesium or manganese salts.
  • sizing is known, for example from the WO 2004/071738 A1 , of the US 3501320 of the DD 63853 A1 , of the US 3211560 A , of the US 2,426,987 A or the JP 2005211983 A .
  • the influence of magnesium or manganese salts on the stability of water-glass-thermally cured molding mixtures of, inter alia, powdery refractory materials does not disclose these because forms and cores of other materials are used there.
  • the hardening of the molding material mixture takes place by removal of the water or condensation still contained.
  • the drying or hardening of the casting mold can also take place under the action of microwaves.
  • inorganic binders also have disadvantages compared to organic binders, for example the known inorganic binders have a low stability of the casting molds produced therewith against high humidity or against water. For a storage of the molded body over a longer period, as usual with organic binders, not secured possible.
  • the US 7770629 B2 proposed a molding material mixture containing a water-based binder in addition to a refractory molding material. A proportion of a particulate metal oxide is added to the molding material mixture. Precipitated silica or fumed silica is preferably used as the particulate metal oxide.
  • the methods described for the production of molds and cores usually also include the application of a refractory mold coating, which is also called sizing, at least on those surfaces of the basic shape, which come into contact with the cast metal.
  • a refractory mold coating which is also called sizing, at least on those surfaces of the basic shape, which come into contact with the cast metal.
  • the purpose of the mold coatings is to influence the molding surface, to improve the casting appearance, to metallurgically influence the casting and / or to avoid casting defects.
  • the commonly used sizing agents contain as base materials e.g. Clays, quartz, kieselguhr, cristobalite, tridymite, aluminum silicate, zirconium silicate, mica, chamotte and also coke and graphite. These bases are the purportive portion of the sizings which cover the mold surface and close the pores against the penetration of the cast metal.
  • the surface of the casting mold can be modified and matched to the properties of the metal to be processed.
  • the size can be used to improve the appearance of the casting by creating a smooth surface because the size compensates for irregularities caused by the size of the grains of the molding material.
  • the size may metallurgically influence the casting by, for example, selectively transferring additives to the casting at the surface of the casting over the size which enhance the surface properties of the casting.
  • the sizings form a layer which chemically isolates the casting mold from the liquid metal during casting. This prevents any adhesion between the casting and the casting mold so that the casting can be removed from the casting mold without difficulty.
  • the sizing can also be used to selectively control the heat transfer between the liquid metal and the casting mold in order, for example, to effect the formation of a specific metal structure by the cooling rate.
  • the curing of the inorganic binder used is nowadays increasingly via a condensation reaction initiated by elevated temperatures, in which the formation of the binder bridges takes place via the splitting off of water.
  • this is a reversible reaction, i. by contact and reaction with water, the bonds can be split again, the extent of this back-reaction is highly dependent on the process parameters for core production.
  • process parameters typically used in series production fast tents, high temperatures
  • the molds lose their strength through contact with water and sometimes also through contact with alcohol, the surface softens and the mold loses its shape.
  • the invention had the object of proposing a sizing, by which the most error-free coating for water glass hardened inorganic cores and molds can be ensured without negatively affecting the stability of the cores or molds and thus the processing and storage.
  • the sizing composition used is, according to a preferred embodiment, provided in the form of a paste or a suspension. Also in this embodiment, the sizing composition contains a carrier liquid.
  • salts of the metals magnesium and / or manganese can be used to achieve the above object.
  • the amount salts are preferably used in the oxidation state +2 or +4. Particular preference is given to using magnesium salts in the oxidation state +2 and the manganese salts in the oxidation state +2.
  • the concentration of the salts is greater than 1% by weight, preferably greater than 3% by weight and particularly preferably greater than 5% by weight, based on the size composition. According to one embodiment, the concentration is limited upwards by the saturation concentration of the respective amount used and type of carrier liquid. According to another embodiment, the maximum concentration is less than 10 wt.%, Based on the Schllchtezusammen GmbH.
  • the sizing composition e.g. as a basecoat or as a topcoat, and desired layer thickness of the coating made from the sizing composition, other characteristic parameters of the sizing composition may be adjusted.
  • esters of formic acid methanoic acid
  • the chain length of the alcohol or alcohol mixture used in the esterification in particular being on average less than 6 and particularly preferably less than 3 carbon atoms.
  • Methyl formate (methyl formate) and ethyl formate (ethyl formate) are particularly preferably used.
  • the alcohol group (s) or some of the alcohol groups to carry one or two further groups, such as ether, hydroxy groups, ester groups or carboxyl groups, or the formic acid through the second or third hydroxyl group is crosslinked, eg by condensation.
  • the total content of the above additives, based on the size composition, is from 1 to 8% by weight, preferably from 2 to 8% by weight and more preferably from 3 to 6% by weight.
  • an additive e.g. "Methyl formate purely" of BASF can be used. It has the CAS number 107-31-3.
  • the carrier liquid can be proportionately or completely formed by water.
  • the carrier liquid is the constituent which is vaporizable at 160 ° C and atmospheric pressure and in this sense, by definition, that which is not solids content.
  • the carrier liquid contains greater than 50% by weight, preferably 75% by weight, in particular greater than 80% by weight, if appropriate greater than 95% by weight of water.
  • the other ingredients in the carrier liquid may be organic solvents.
  • Suitable solvents are alcohols, including polyhydric alcohols and polyether alcohols.
  • Exemplary alcohols are ethanol, n-propanol, isopropanol, butanol and glycol.
  • the solids content of the ready-to-use sizing composition is preferably set in the range from 10 to 85% by weight, or in the sold form (before dilution), in particular from 30 to 70% by weight.
  • the sizing composition comprises at least one powdered refractory material .
  • This refractory material serves to close the pores in a mold against the penetration of the liquid metal.
  • the refractory thermal insulation between the mold and liquid metal is achieved by the refractory thermal insulation between the mold and liquid metal.
  • refractory material conventional refractory materials can be used in metal casting.
  • Suitable refractory materials are quartz, aluminum oxide, zirconium oxide, aluminum silicates, such as pyropyllite, kyanite, andalusite or chamotte, zirconium, ciconsilicates, olivine, talc, mica, coke, feldspar, diatomite, calcined kaolins, kaolinite, metakaolinite, iron oxide and / or bauxite ,
  • the refractory material is provided in powder form.
  • the grain size is chosen so that a stable structure is produced in the coating and that the sizing can preferably be distributed without problem on the wall of the casting mold with a spray device.
  • the refractory material has an average particle size (measured by means of light scattering in accordance with DIN / ISO 13320) in the range from 0.1 to 500 ⁇ m, particularly preferably in the range from 1 to 200 ⁇ m.
  • materials which have a melting point which is at least 200 ° C. above the temperature of the liquid metal and, independently of this, do not react with the metal are suitable as the refractory material.
  • the fraction of the refractory material (in each case contributing only to the solids content), based on the solids content of the sizing composition, is preferably greater than 70% by weight, preferably greater than 80% by weight, particularly preferably greater than 85% by weight.
  • the fraction of the refractory material is chosen to be less than 70% by weight, according to a further embodiment less than 60% by weight and according to a further embodiment less than 50% by weight.
  • the sizing may comprise at least one adjusting means according to one embodiment.
  • the adjusting agent causes an increase in the viscosity of the size, so that the solid components of the size in the suspension do not or only to a small extent decrease.
  • organic and inorganic materials or mixtures of these materials can be used.
  • Suitable inorganic adjusting agents are, for example, strongly swellable clays, such as sodium bentonite.
  • organic thickening agents may alternatively or additionally be selected, since these can be dried to the extent that they hardly give off any more water upon contact with the liquid metal after application of the protective coating.
  • Suitable organic solvents are, for example, swellable polymers, such as carboxymethyl, methyl, ethyl, hydroxyethyl and hydroxypropyl cellulose, mucilages, polyvinyl alcohols, Polyvlnylpyrrolldon, pectin, gelatin, agar agar, polypeptides and / or alginates.
  • the proportion of the adjusting agent, based on the total size composition is preferably selected to be from 0.1 to 5% by weight, preferably from 0.5 to 3% by weight, particularly preferably from 1 to 2% by weight.
  • the size comprises as further constituent at least one binder .
  • the binder allows a better fixation of the size or of the protective coating produced from the size on the wall of the mold.
  • the binder increases the mechanical stability of the protective coating so that less erosion is observed under the action of the liquid metal. Vorzugswelse cures the binder irreversibly, so that an abrasion-resistant coating is obtained.
  • binders which do not soften on contact with atmospheric moisture. All binders which are used in sizing can be contained per se. In this case, both inorganic and organic binders can be used.
  • clays can be used as binders, in particular bentonite and / or kaolin.
  • the proportion of the binder is preferably selected in the range of 0.1 to 20 wt .-%, particularly preferably 0.5 to 5 wt .-%, based on the solids content of the sizing composition.
  • the size contains a proportion of graphite .
  • the proportion of graphite is preferably selected in the range of 1 to 30 wt .-%, particularly preferably 5 to 15 wt .-%, based on the solids content of the size composition.
  • Graphite has a favorable effect on the surface quality of castings during iron casting.
  • the sizing composition may also comprise further components customary for sizing, for example wetting agents, defoamers, pigments, dyes or biocides.
  • the proportion of these further constituents in the ready-to-use coating composition is preferably less than 10% by weight, preferably less than 5% by weight and more preferably less than 1% by weight.
  • Suitable wetting agents are , for example, anionic and non-anionic surfactants, in particular those having an HSB value of at least 7.
  • An example of such a wetting agent is disodium dioctyl sulfosuccinate.
  • the wetting agent is preferably used in an amount of 0.01 to 1 wt .-%, preferably 0.05 to 0.3 wt .-%, based on the ready-to-use sizing composition.
  • Defoamers can be used to prevent foaming in the preparation of the sizing composition or in applying it. Foaming on application of the sizing composition can result in uneven layer thickness and voids in the coating.
  • defoamers for example, silicone or mineral oil can be used.
  • the defoamer is preferably present in an amount of from 0.01 to 1% by weight, preferably from 0.05 to 0.3% by weight, based on the ready-to-use sizing composition.
  • pigments and dyes may be used in the sizing composition. These are added in order to achieve a different contrast, for example between different sizes, or to bring about a greater separation effect of the size of the casting.
  • pigments are red and yellow iron oxide and graphite.
  • dyes are commercially available dyes such as the Luconyl® color series of BASF AG, Ludwigshafen, DE.
  • the dyes and pigments are preferably contained in an amount of 0.01 to 10 wt .-%, preferably from 0.1 to 5 wt .-%, based on the solids content of the sizing composition.
  • the sizing composition contains a biocide to prevent bacterial attack, thereby avoiding a negative impact on the rheology and binding power of the binding agents.
  • the carrier liquid contained in the sizing composition is formed substantially in water with respect to the weight, that is, the sizing composition is provided in the form of a so-called water sizing.
  • elicited biocides are formaldehyde, 2-methyl-4-isothiazolin-3-one (MIT), 5-chloro-2-methyl-4-iosthiazolin-3-one (CIT) and 1,2-benzisothiazolin-3-one (BIT).
  • MIT, BIT or a mixture thereof are used.
  • the biocides are usually used in an amount of from 10 to 1000 ppm, preferably from 50 to 500 ppm, based on the weight of the ready-to-use sizing composition.
  • the sizing composition may contain further constituents customary for sizing.
  • the heat composition can be prepared by conventional methods.
  • the sizing composition may be prepared by initially introducing water and breaking up a clay acting as a sizing agent using a high shear stirrer. Subsequently, the refractory components, pigments and dyes and the metallic additive are stirred until a homogeneous mixture is formed. Finally, wetting agents, antifoams, biocides and binders are added.
  • the sizing composition may be prepared and sold as a ready-to-use sizing.
  • the size can also be produced and sold in concentrated form.
  • the amount of carrier liquid necessary to adjust the desired viscosity and density of the size is added.
  • the sizing composition may also be provided and sold in the form of a kit, for example where the solid components and the solvent component are present side by side in separate containers.
  • the solid components can be provided as a powdery solid mixture in a separate container.
  • liquid components to be used e.g. Binders, wetting agents, wetting agents / defoamers, pigments, dyes and biocides
  • the solvent component may comprise either the optionally additional components to be used, e.g. in a common container, or it may be separate from other optional components in a separate container.
  • the appropriate amounts of the solid component, the optional further components and the solvent component are mixed together.
  • the sizing compositions are useful for coating slip forms .
  • the term "mold” includes all types of bodies necessary to make a casting, such as cores, molds and molds.
  • the use of the size compositions according to the invention also includes partial coating of casting molds.
  • the sizings are used for metal working molds obtainable from inorganic molding material mixtures comprising at least one refractory molding base, a water glass based binder, and preferably a portion of a metal oxide selected from the group of silica, especially amorphous silica, alumina, titania or zinc oxide and mixtures thereof, this preferably being in the form of a wafer and in particular having particle sizes of less than 300 ⁇ m (sieve analysis).
  • Amorphous silica is available, for example, via precipitation processes starting from water glass, which is obtainable by digesting quartz sand with sodium carbonate or potassium carbonate. Depending on the process conditions, so-called SIO 2 is called precipitated silica. Another important production variant is the production of so-called pyrogenic SiO 2 in a blast gas flame, starting from liquid chlorosilanes such as silicon tetrachloride.
  • the invention relates to a process for the preparation of glazed molds for metal processing with application of the sizes to the above partially or completely cured inorganic molding material mixtures.
  • the application or provision of the sizes can be carried out as follows: When dipping as an application method, the mold, in the mold cavity of which optionally a primer coating has been applied, is immersed for about 2 seconds to 2 minutes in a container filled with a ready-to-use, sizing composition. The slip mold is then removed from the sizing composition and excess sizing composition drained from the casting mold. The tent, which takes the expiration of the excess sizing composition after dipping, depends on the flow behavior of the sizing composition used.
  • the sizing composition is filled in a dilute state in a pressure pot.
  • the sizing can be pressed into a spray gun via the overpressure to be set, where it is sprayed with the aid of separately adjustable atomizing air.
  • the conditions are preferably selected so that the pressure for sizing composition and atomizing air is adjusted at the gun such that the sprayed sizing composition still wet on the mold or the core, but gives a uniform application.
  • the casting mold in the mold cavity of which a base coat has optionally been applied, is poured over with the aid of a hose, a lance or similar instruments with a ready-to-use sizing composition.
  • the mold is completely covered with the sizing composition, the excess sizing composition drains from the mold.
  • the tent which takes advantage of the drainage of the excess size composition after flooding, depends on the flow behavior of the sizing composition used.
  • the sizing can also be applied by brushing .
  • the carrier liquid contained in the size is then evaporated, so that a dry size coat is obtained.
  • any conventional drying method can be used, such as air drying, dehumidified air drying, microwave or infrared radiation drying, convection oven drying, and similar methods.
  • the coated casting mold is dried at 20 to 250 ° C, preferably at 50 to 180 ° C, in a convection oven.
  • the sizing composition is preferably dried by burning off the alcohol or alcohol mixture.
  • the coated casting mold is additionally heated by the heat of combustion.
  • the coated casting mold is dried in the air without further treatment or using microwaves.
  • the size can be applied in the form of a single layer or else in the form of a plurality of layers arranged one above the other.
  • the individual layers in their composition can be the same or different.
  • a base coat can first be prepared from a commercially available size which does not contain any metallic additive used according to the invention.
  • a primer coating for example, water-based or alcohol-based sizing can be used. But it is also possible to produce all layers of the sizing composition. However, the layer which later comes into contact with the liquid metal is always made from the size used according to the invention.
  • each individual layer can be completely or partially dried after application.
  • the coating prepared from the sizing composition preferably has a dry film thickness of at least 0.1 mm, preferably at least 0.2 mm, more preferably at least 0.45 mm, most preferably at least 0.55 mm. According to one embodiment, the thickness of the coating is chosen to be less than 1.5 mm.
  • the dry layer thickness here is the layer thickness of the dried coating, which was obtained by drying the sizing composition by substantially complete removal of the solvent component and optionally subsequent curing.
  • the dry layer thickness of the base coat and the top coat are preferably determined by measurement with the wet film thickness comb.
  • the casting mold can then be completely assembled.
  • the casting is preferably carried out for the production of iron and cast steel bodies.
  • the core sizes 1 to 3 used have the compositions given in Table 1 to 3.
  • Table 1 Composition of the sizes Simple 1 Simple 2 Simple 3 component % By weight % By weight % By weight water 31 31 31.0 MnCl2 5.0 - MgSO4 - 5.0 0.5 Zirconium flour 45 ⁇ m 19.5 19.5 21.0 Actigel 208 1.0 1.0 1.0 1.0 PVA solution (25%) 1.5 1.5 1.5 Satintone W® 17 17 18 Surfynol® SEF (wetting agent 1) 0.2 0.2 0.2 Dynol® 604 (wetting agent 2) 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Fo
  • the mold casting size was prepared as follows: Water is introduced and the salts are dissolved therein. The clay is then disrupted by using a high shear stirrer for at least 15 minutes.
  • the refractory components, pigments and dyes are stirred for at least 15 minutes until a homogeneous mixture is formed.
  • additives such as wetting agents, defoamers and preservatives and the binder are stirred.
  • the manganese chloride contained in the size 1 or the magnesium sulfate contained in size 2 when used on inorganic cores and molds, significantly reduces the dissolution or softening of the inorganic binder in the surface.
  • a higher stability of the sized cores compared to conventional sizes can be determined.
  • the effect is based on the fact that the water contained in the sizing upon contact with the cured inorganic binder must absorb the ions formed during the dissolution process. However, if the water already contains an unusually high ion content, the solubility product increases and the uptake of further ions is impeded or prevented.
  • the solubilized salts in the sizing contribute to the prevention of destabilization of the inorganic cores and molds during the sizing process.
  • a comparable behavior can also be achieved with chemically related salts of the metals magnesium and manganese.
  • Georg Fischer test strip illustrates the behavior of the sized test specimens on thicker core geometries
  • long cores illustrates the behavior of the sized test specimens on thin geometries.
  • Georg Fischer test bars are cuboid test bars measuring 150 mm x 22.36 mm x 22.36 mm.
  • the long cores have dimensions of 13 mm x 20 mm x 235 mm.
  • the composition of the molding material mixture is given in Table 3.
  • the Georg Fischer test bars were prepared as follows: The components listed in Table 3 were mixed in a laboratory paddle mixer (Vogel & Schemmann AG, Hagen, DE). For this purpose, initially the quartz sand was introduced and added with stirring the water glass. As a water glass, a sodium water glass was used, which had proportions of potassium. The modulus SiO 2 : M 2 O of the water glass was about 2.2, where M is the sum of sodium and potassium. After stirring the mixture for one minute, amorphous silica was added, if necessary, with further stirring. The amorphous silica is pyrogenic silica from RW silicon. The mixture was then stirred for an additional 1 minute.
  • the molding material mixture was transferred to the storage bunker of an H 2.5 hot-box core shooter from Röperwerk-G manmaschinen GmbH, Viersen, DE, whose mold had been heated to 180.degree.
  • the molding material mixture was introduced into the mold by means of compressed air (5 bar) and remained in the mold for a further 35 seconds.
  • hot air (2 bar, 150 ° C on entering the mold) was passed through the mold during the last 20 seconds. The mold was opened and the test bars removed.
  • the coating compositions were applied to the test bars by dipping, the application parameters are listed in Table 2.
  • the test bars were coated either immediately after removal from the mold or after a 30 minute cooling time.
  • the coated test bars were stored after application of the coating in a drying oven for 30 minutes at 150 ° C.
  • test bars were placed in a Georg Fischer strength tester equipped with a 3-point bending device (DISA Industrie AG, Schaffhausen, CH), and the force was measured, which leads to the breakage of the test bars.
  • salts of the metals magnesium or manganese can be used.
  • the manganese salts are used with a valency of +4.
  • Particularly preferred are magnesium salts having a valency of +2 and the manganese salts having a valency of +2.
  • Sulfate ion is preferably used as anions, particularly preferably the monovalent chloride ion is used as anions.
  • the concentration of the salts is in particular between 1% and the respective saturation concentration, preferably between 3% and the respective saturation concentration, particularly preferably between 5% and the respective saturation concentration.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Mold Materials And Core Materials (AREA)
  • Surface Treatment Of Glass Fibres Or Filaments (AREA)
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EP12780402.9A 2011-10-07 2012-10-05 Beschichtungsmassen für anorganische giessformen und kerne enthaltend salze und deren verwendung Active EP2763807B1 (de)

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Application Number Priority Date Filing Date Title
DE102011115025A DE102011115025A1 (de) 2011-10-07 2011-10-07 Beschichtungsmassen für anorganische Gießformen und Kerne enthaltend Salze und deren Verwendung
PCT/DE2012/000972 WO2013050022A2 (de) 2011-10-07 2012-10-05 Beschichtungsmassen für anorganische giessformen und kerne enthaltend salze und deren verwendung

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EP2763807A2 EP2763807A2 (de) 2014-08-13
EP2763807B1 true EP2763807B1 (de) 2018-12-26

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US (1) US20140352910A1 (pt)
EP (1) EP2763807B1 (pt)
JP (1) JP2014534074A (pt)
KR (1) KR20140073576A (pt)
CN (1) CN103857481A (pt)
BR (1) BR112014008373A2 (pt)
DE (1) DE102011115025A1 (pt)
IN (1) IN2014KN00956A (pt)
MX (1) MX2014004213A (pt)
RU (1) RU2014118126A (pt)
WO (1) WO2013050022A2 (pt)
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102011115024A1 (de) * 2011-10-07 2013-04-11 Ask Chemicals Gmbh Beschichtungsmassen für anorganische Gießformen und Kerne umfassend Ameisensäureester und deren Verwendung
US20150050816A1 (en) * 2013-08-19 2015-02-19 Korea Atomic Energy Research Institute Method of electrochemically preparing silicon film
KR101527909B1 (ko) * 2014-12-16 2015-06-10 한국생산기술연구원 주조용 무기 바인더 조성물
DE102016015852B4 (de) 2016-06-30 2024-05-29 Refratechnik Holding Gmbh Verwendung eines wärmedämmenden Formkörpers
DE102016112044B4 (de) 2016-06-30 2019-01-03 Refratechnik Holding Gmbh Verwendung einer wärmedämmenden Platte zur Isolation von Metallschmelzen gegenüber der Atmosphäre oder einem metallurgischen Gefäß
DE102017107658A1 (de) 2017-01-04 2018-07-05 HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung Schlichtezusammensetzung für die Gießereiindustrie, enthaltend partikuläres, amorphes Siliziumdioxid und Säure
DE102017107655A1 (de) * 2017-01-04 2018-07-05 HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung Verwendung einer Säure enthaltenden Schlichtezusammensetzung in der Gießereiindustrie
DE102017107657A1 (de) 2017-01-04 2018-07-05 HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung Schlichtezusammensetzung, umfassend organische Esterverbindungen und partikuläres, amorphes Siliziumdioxid, zur Verwendung in der Gießereiindustrie
CN108752629B (zh) * 2018-06-06 2020-10-02 曹立军 一种光散射粒子的制备方法
DE102018117651A1 (de) 2018-07-20 2020-01-23 Ask Chemicals Gmbh Schlichtezusammensetzung für Gießformen für den Metallguss deren Verwendung sowie mit der Schlichtezusammensetzung versehene Gießform
DE102019116702A1 (de) * 2019-06-19 2020-12-24 Ask Chemicals Gmbh Geschlichtete Gießformen erhältlich aus einer Formstoffmischung enthaltend ein anorganisches Bindemittel und Phosphat- und oxidische Borverbindungen, ein Verfahren zu deren Herstellung und deren Verwendung

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2426987A (en) * 1942-11-13 1947-09-09 Aluminum Co Of America Mold coating
US3211560A (en) * 1961-12-18 1965-10-12 Caterpillar Tractor Co Mold wash composition and casting mold coated therewith
DD63853A1 (de) * 1967-10-04 1968-09-20 Schlichte für dauerformen sum giessen von leicht- und buntmetallen
JP2005211983A (ja) * 2004-02-02 2005-08-11 Kao Corp 鋳造用塗型剤組成物

Family Cites Families (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB641583A (en) * 1948-07-28 1950-08-16 Neil Douglas Gordon Robertson Improvements in or relating to permanent mould casting
GB782205A (en) 1955-03-07 1957-09-04 Foundry Services Ltd Improvements in or relating to sand cores
US3501320A (en) * 1967-11-20 1970-03-17 Gen Motors Corp Die casting core
AT301059B (de) * 1970-06-17 1972-08-25 Reichhold Chemie Ag Schlichte für Gießereiformen und Kerne
US3932201A (en) * 1975-02-24 1976-01-13 Morton-Norwich Products, Inc. Magnesium oxide coating composition and process
SU529883A1 (ru) * 1975-03-07 1976-09-30 Харьковский Ордена Ленина Политехнический Институт Им.В.И.Ленина Огнеупорное покрытие дл поддонов
FR2314901A1 (fr) * 1975-06-16 1977-01-14 Ball Corp Composition anti-adhesive pour moules, comprenant du bisulfure de tungstene
SU1199425A1 (ru) * 1983-05-25 1985-12-23 Харьковский Ордена Ленина Политехнический Институт Им.В.И.Ленина Состав дл получени покрыти на изложницах
SU1245620A1 (ru) * 1984-10-24 1986-07-23 Уральский Ордена Трудового Красного Знамени Научно-Исследовательский Институт Черных Металлов Состав дл термоизол ционного покрыти на электротехнических стал х
SU1289582A1 (ru) * 1985-09-03 1987-02-15 Украинский научно-исследовательский институт металлов Состав дл получени противопригарного покрыти на литейных формах
CN1018338B (zh) * 1990-10-24 1992-09-23 湖南省电力机械厂 镁砂铸钢涂料
JPH06190503A (ja) * 1992-12-28 1994-07-12 Ube Ind Ltd 砂中子の製造方法
US5382289A (en) 1993-09-17 1995-01-17 Ashland Oil, Inc. Inorganic foundry binder systems and their uses
US5474606A (en) 1994-03-25 1995-12-12 Ashland Inc. Heat curable foundry binder systems
DE19925167A1 (de) 1999-06-01 2000-12-14 Luengen Gmbh & Co Kg As Exotherme Speisermasse
DE29925010U1 (de) 1999-10-26 2008-09-04 Mincelco Gmbh Wasserglasgebundener Kernformstoff
DE10305612B4 (de) * 2003-02-11 2005-04-07 Ashland-Südchemie-Kernfest GmbH Beschichtungsmassen für Gusskerne
DE102004042535B4 (de) * 2004-09-02 2019-05-29 Ask Chemicals Gmbh Formstoffmischung zur Herstellung von Gießformen für die Metallverarbeitung, Verfahren und Verwendung
DE102004054048A1 (de) * 2004-11-05 2006-05-11 Basf Ag Beschichtungsmassen
EP1922368B1 (de) * 2005-08-18 2016-12-21 Clariant Finance (BVI) Limited Beschichtungsmassen enthaltend mischoxid-nanopartikel bestehend aus 50-99,9 gew% al2o3 und 0,1-50 gew% oxiden von elementen der i. oder ii. hauptgruppe des periodensystems
CN101003073A (zh) * 2006-01-16 2007-07-25 刘玉满 消失模及砂型铸造水基涂料复合粉状添加剂
DE102006031191A1 (de) * 2006-07-04 2008-01-10 Dracowo Forschungs- Und Entwicklungs Gmbh Anorganische Kernsandbinder und Schlichten für den Aluminiumguss und ihre weitere Verwendung als Düngemittel
DE102006049379A1 (de) * 2006-10-19 2008-04-24 Ashland-Südchemie-Kernfest GmbH Phosphorhaltige Formstoffmischung zur Herstellung von Giessformen für die Metallverarbeitung
DE102007051850A1 (de) * 2007-10-30 2009-05-07 Ashland-Südchemie-Kernfest GmbH Formstoffmischung mit verbesserter Fliessfähigkeit
UA101663C2 (ru) * 2008-05-28 2013-04-25 Ашланд-Зюдхеми-Кернфест Гмбх Покрытие для литейных форм и стержней для предотвращения образования раковин на поверхностях
KR100949830B1 (ko) * 2008-07-29 2010-03-29 김종식 녹고정제 조성물
CN101906269A (zh) * 2009-06-08 2010-12-08 安集微电子科技(上海)有限公司 一种金属化学机械抛光的浆料及其使用方法
CN102001850B (zh) * 2009-08-28 2013-04-03 斯富迈材料科技(上海)有限公司 一种轻质发泡防火板及其制备方法
CN101775873B (zh) * 2009-12-29 2012-03-21 广州市木易木制品有限公司 一种轻质珍珠岩复合墙体板及其制造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2426987A (en) * 1942-11-13 1947-09-09 Aluminum Co Of America Mold coating
US3211560A (en) * 1961-12-18 1965-10-12 Caterpillar Tractor Co Mold wash composition and casting mold coated therewith
DD63853A1 (de) * 1967-10-04 1968-09-20 Schlichte für dauerformen sum giessen von leicht- und buntmetallen
JP2005211983A (ja) * 2004-02-02 2005-08-11 Kao Corp 鋳造用塗型剤組成物

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WO2013050022A2 (de) 2013-04-11
BR112014008373A2 (pt) 2017-04-11
EP2763807A2 (de) 2014-08-13
CN103857481A (zh) 2014-06-11
JP2014534074A (ja) 2014-12-18
KR20140073576A (ko) 2014-06-16
IN2014KN00956A (pt) 2015-10-09
MX2014004213A (es) 2014-05-28
ZA201402176B (en) 2015-04-29
US20140352910A1 (en) 2014-12-04
WO2013050022A3 (de) 2013-05-30
DE102011115025A1 (de) 2013-04-11

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