EP2392424B1 - Procédé de fabrication de moules pour le traitement du métal, moules fabriqués selon ce procédé et leur utilisation - Google Patents

Procédé de fabrication de moules pour le traitement du métal, moules fabriqués selon ce procédé et leur utilisation Download PDF

Info

Publication number
EP2392424B1
EP2392424B1 EP11006910.1A EP11006910A EP2392424B1 EP 2392424 B1 EP2392424 B1 EP 2392424B1 EP 11006910 A EP11006910 A EP 11006910A EP 2392424 B1 EP2392424 B1 EP 2392424B1
Authority
EP
European Patent Office
Prior art keywords
process according
material mixture
casting
molding material
proportion
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.)
Active
Application number
EP11006910.1A
Other languages
German (de)
English (en)
Other versions
EP2392424A1 (fr
Inventor
Günter Weicker
Diether Koch
Jens Müller
Udo Skerdl
Henning Rehse
Anton Gienic
Reinhard Stötzel
Thomas Dünnwald
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ASK Chemicals GmbH
Original Assignee
ASK Chemicals GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=35701554&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP2392424(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by ASK Chemicals GmbH filed Critical ASK Chemicals GmbH
Priority to PL11006910T priority Critical patent/PL2392424T3/pl
Priority to SI200532269T priority patent/SI2392424T1/sl
Publication of EP2392424A1 publication Critical patent/EP2392424A1/fr
Application granted granted Critical
Publication of EP2392424B1 publication Critical patent/EP2392424B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • B22C1/18—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
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents

Definitions

  • the invention relates to a process for the production of casting molds for metal processing, which comprises at least one free-flowing refractory molding base material and a water glass-based binder. Furthermore, the invention relates to a method for the production of molds for metal processing using the molding material mixture as well as a mold obtained by the method.
  • Molds for the production of metal bodies are essentially produced in two versions.
  • a first group form the so-called cores or forms. From these, the casting mold is assembled, which essentially represents the negative mold of the casting to be produced.
  • a second group form hollow bodies, so-called feeders, which act as a compensation reservoir. These take up liquid metal, whereby appropriate measures are taken to ensure that the metal lasts longer the liquid phase remains as the metal which is in the mold forming the negative mold. If the metal solidifies in the negative mold, liquid metal can flow out of the compensation reservoir to compensate for the volume contraction that occurs when the metal solidifies.
  • Casting molds are made of a refractory material, such as quartz sand, whose grains are connected after molding of the mold by a suitable binder to ensure sufficient mechanical strength of the mold.
  • a refractory molding material which has been treated with 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.
  • Molds must meet different requirements. During the casting process itself, they must first of all have sufficient stability and temperature resistance in order to receive the liquid metal in the mold formed from one or more casting molds. After the start of the solidification process, the mechanical stability of the mold is ensured by a solidified metal layer, which forms along the walls of the mold. The material of the casting mold must now decompose under the influence of the heat given off by the metal in such a way that it loses its mechanical strength, that is to say the cohesion between individual particles of the refractory material is removed. This is achieved, for example, by decomposing the binder under heat. After cooling, the solidified casting is shaken, ideally, the material of the casting molds again to a fine Sand breaks down, which can be poured out of the cavities of the metal mold.
  • 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.
  • organic binders are often used for the production of casting molds, in which the curing reaction is accelerated by a gaseous catalyst or cured by reaction with a gaseous hardener. These methods are referred to as "cold-box" methods.
  • Ashland cold box process An example of the production of molds using organic binders is the so-called Ashland cold box process. It is a two-component system. The first component consists of the solution of a polyol, usually a phenolic resin. The second component is the solution of a polyisocyanate.
  • the curing reaction of polyurethane binders is a polyaddition, ie a reaction without elimination of By-products, such as water.
  • advantages of this cold-box process include good productivity, dimensional accuracy of the molds, and good engineering properties such as the strength of the molds, the processing time of the mixture of mold base and binder, etc.
  • Hot-curing organic processes include the hot-box process based on phenolic or furan resins, the warm box process based on furan resins, and the croning process based on phenolic novolac resins.
  • liquid resins are processed with a latent curing agent which is only effective at elevated temperatures to form a molding material mixture.
  • mold base materials such as quartz, chrome ore, zirconium, etc., are coated at a temperature of about 100 to 160 ° C with a liquid at this temperature phenol novolac resin. Hexamethylenetetramine is added as a reaction partner for the subsequent curing.
  • the shaping and curing take place in heatable tools, which are heated to a temperature of up to 300 ° C.
  • all organic systems have in common that they thermally decompose when the liquid metal is poured into the mold, releasing pollutants such as benzene, toluene, xylenes, phenol, formaldehyde and higher, sometimes unidentified cracking products.
  • pollutants such as benzene, toluene, xylenes, phenol, formaldehyde and higher, sometimes unidentified cracking products.
  • pollutants such as benzene, toluene, xylenes, phenol, formaldehyde and higher, sometimes unidentified cracking products.
  • binder systems which are based on inorganic materials or contain at most a very small proportion of organic compounds.
  • 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 782,205 described in which an alkali water glass is used as a binder, which can be cured by the introduction of CO 2 . In the DE 199 25 167 will describe an exothermic feeder mass containing an alkali silicate as a binder. Furthermore, binder systems have been developed which are self-curing at room temperature.
  • thermosetting binder systems are for example from US 5,474,606 in which a binder system consisting of alkali water glass and aluminum silicate is described.
  • Inorganic binders have the disadvantage, in comparison to organic binders, that the casting molds produced therefrom have relatively low strengths. This is especially evident immediately after the removal of the mold from the tool. Good strength at this time, however, are particularly important for the production of complicated, thin-walled moldings and their safe handling. The reason for the low strength is primarily that the molds still contain residual water from the binder. Longer dwell times in the hot, closed tool only help to a limited extent because the water vapor can not escape sufficiently. To complete the drying of the molds as complete as possible will reach in the WO 98/06522 proposed to leave the molding material mixture after molding only in a tempered core box so long that forms a dimensionally stable and sustainable edge shell. After opening the core box, the mold is removed and then completely dried under the action of microwaves. However, the additional drying is complex, prolongs the production time of the molds and contributes, not least by the energy costs, significantly to the increase in the cost of the manufacturing process.
  • an alkali metal hydroxide in particular sodium hydroxide solution
  • a particulate metal oxide which can form a metalate in the presence of the alkali metal hydroxide solution.
  • the particles are dried after a layer of the metal has formed at the edge of the particles. At the core of the particles remains a section in which the metal oxide was not reacted.
  • a dispersed silica or finely divided titanium oxide or zinc oxide is preferably used.
  • WO 94/14555 describes a molding material mixture, which is also suitable for the production of molds and which contains a binder in addition to a refractory molding material, which consists of a phosphate or borate glass, wherein the mixture further contains a finely divided refractory material.
  • a refractory molding material which consists of a phosphate or borate glass
  • the mixture further contains a finely divided refractory material.
  • silicon dioxide can also be used as the refractory material.
  • 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 Si0 2 / M 2 0 of 2.5 to 3.5 and a solids content of 20 to 40%.
  • the binder system also 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.
  • a suitable refractory material such as quartz sand
  • the hardening of the molding material mixture takes place by removal of the water still contained.
  • the drying or hardening of the casting mold can also take place under the action of microwaves.
  • the previously known molding material mixtures for the production of casting molds still have room for an improvement in the properties, for example, in terms of the strength of the molds produced and in terms of their resistance to atmospheric moisture during storage for a long period. Furthermore, the goal is to achieve a high quality of the surface of the casting after the casting, so that the finishing of the surface can be carried out with little effort.
  • the molding material mixture should allow the production of casting molds, with which castings can be produced, which have a high quality of the surface, so that only a small finishing of the surfaces is required.
  • the molding material mixture for the production of casting molds for metal processing comprises at least: a refractory molding base material; and a water glass based binder.
  • a refractory molding base material can be used for the production of molds usual materials. Suitable examples are quartz or zircon sand. Furthermore, fibrous refractory mold bases are suitable, such as chamotte fibers. Other suitable refractory mold bases are, for example, olivine, chrome ore sand, vermiculite.
  • artificial molding materials can also be used as refractory molding base materials, for example aluminum silicate hollow spheres (so-called microspheres), glass beads, glass granules or spherical ceramic molding base materials known under the name "Cerabeads" or "Carboaccucast”.
  • These spherical ceramic mold bases contain as minerals, for example mullite, corundum, ⁇ -cristobalite in different proportions. They contain as essential proportions alumina and silica. Typical compositions contain, for example, Al 2 O 3 and SiO 2 in approximately equal proportions. In addition, other constituents may be present in proportions of ⁇ 10%, such as TiO 2 , Fe 2 O 3 .
  • the diameter of the microspheres is preferably less than 1000 ⁇ m, in particular less than 600 ⁇ m.
  • These artificial molding bases are not of natural origin and may have been subjected to a special molding process, such as in the production of aluminum silicate microbubbles, glass beads or spherical ceramic molding bases.
  • Glass materials are particularly preferably used as refractory artificial mold base materials. These are used in particular either as glass beads or as glass granules. Conventional glasses can be used as the glass, with glasses showing a high melting point being preferred. Suitable examples are glass beads and / or glass granules, which is made of glass breakage. Also suitable are borate glasses. The composition of such glasses is exemplified in the table below. Table: Composition of glasses component glass breakage borate glass SiO 2 50 - 80% 50 - 80% Al 2 O 3 0 -15% 0 - 15% Fe 2 O 3 ⁇ 2% ⁇ 2% M II O 0 - 25% 0 - 25% M I 2 O 5 - 25% 1 - 10% B 2 O 3 ⁇ 15% Otherwise. ⁇ 10% ⁇ 10% M II : alkaline earth metal, eg Mg, Ca, Ba M I : alkali metal, eg Na, K
  • glasses listed in the table it is also possible to use other glasses whose content of the abovementioned compounds lies outside the ranges mentioned.
  • special glasses can be used which contain other elements or their oxides in addition to the aforementioned oxides.
  • the diameter of the glass beads is preferably less than 1000 ⁇ m, in particular less than 600 ⁇ m.
  • the preferred proportion of the artificial molding base materials is at least about 3 wt .-%, more preferably at least 5 wt .-%, particularly preferably at least 10 wt .-%, preferably at least about 15 wt .-%, particularly preferably at least about 20 Wt .-%, 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. These glasses contain dissolved sodium or potassium silicates and can be prepared by dissolving vitreous potassium and sodium silicates in water.
  • the water glass preferably has a modulus SiO 2 / M 2 0 in the range of 1.6 to 4.0, in particular 2.0 to 3.5, wherein M is sodium and / or potassium.
  • the water glasses preferably have a solids content in the range of 30 to 60% by weight. The solids content refers to the amount of SiO 2 and M 2 O contained in the water glass.
  • the molding material mixture contains a proportion of a particulate metal oxide.
  • the particle size of these metal oxides is preferably less than 300 microns, preferably less than 200 microns, more preferably less than 100 microns.
  • the particle size can be determined by sieve analysis.
  • the sieve residue on a sieve with a mesh width of 63 ⁇ m is less than 10% by weight, preferably less than 8% by weight.
  • the particulate metal oxide is synthetically produced amorphous silica, preferably using precipitated silica and / or fumed silica.
  • Precipitated silica is obtained by reaction of an aqueous alkali metal silicate solution with mineral acids. The resulting precipitate is then separated, dried and ground.
  • Fumed silicas are understood to mean silicic acids which are obtained by coagulation from the gas phase at high temperatures.
  • the production of fumed silica can be carried out, for example, by flame hydrolysis of silicon tetrachloride or in an electric arc furnace by reduction of quartz sand with coke or anthracite to silicon monoxide gas with subsequent oxidation to silica.
  • the pyrogenic silicas produced by the arc furnace process may still contain carbon.
  • Precipitated silica and fumed silica are equally well suited for the molding material mixture according to the invention. These silicas are hereinafter referred to as "synthetic amorphous silica
  • the molding material mixture according to the invention represents an intensive mixture of at least the constituents mentioned.
  • the particles of the refractory molding material are preferably coated with a layer of the binder.
  • evaporating the water present in the binder about 40 to 70 wt .-%, based on the weight of the binder
  • a solid Cohesion between the particles of the refractory base molding material can be achieved.
  • the binder i. the water glass as well as the particulate metal oxide, i. the synthetic amorphous silica is preferably contained in the molding material mixture in a proportion of less than 20% by weight. If massive molding base materials are used, such as quartz sand, the binder is preferably present in a proportion of less than 10 wt .-%, preferably less than 8 wt .-%, more preferably less than 5 wt .-%. If refractory mold bases are used which have a low density, such as the hollow microspheres described above, the proportion of binder increases accordingly.
  • the particulate metal oxide i.
  • the synthetic amorphous silica based on the weight of the binder, is preferably contained in a proportion of 2 to 60% by weight, preferably between 3 and 50% by weight, particularly preferably between 4 and 40% by weight.
  • the ratio of water glass to particulate metal oxide, ie, synthetic amorphous silica can be varied within wide ranges. This offers the advantage of improving the initial strength of the casting mold, ie the strength immediately after removal from the hot tool, and the moisture resistance, without substantially affecting the ultimate strengths, ie the strengths after cooling of the casting mold, over a waterglass binder without amorphous silica. 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 these after the production of the casting mold or to assemble them with other casting molds. On the other hand, the final strength after curing should not be too high to cause difficulties in curing
  • Binder decomposition after casting to avoid i.
  • the molding material should be able to be easily removed after casting from cavities of the mold.
  • the molding material contained in the molding material mixture may contain at least a proportion of hollow microspheres.
  • the diameter of the hollow microspheres is normally in the range of 5 to 500 ⁇ m, preferably in the range from 10 to 350 ⁇ m and the thickness of the shell is usually in the range of 5 to 15% of the diameter of the microspheres.
  • These microspheres have a very low specific gravity, so that the molds produced using hollow microspheres have a low weight.
  • Particularly advantageous is the insulating effect of the hollow microspheres.
  • the hollow microspheres are therefore used in particular for the production of molds, if they are to have an increased insulating effect.
  • Such casting molds are, for example, the feeders already described in the introduction, which act as a compensation reservoir and contain liquid metal, wherein the metal should be kept in a liquid state until the metal filled into the mold has solidified.
  • Another application of casting molds containing hollow microspheres are, for example, sections of a casting mold which correspond to particularly thin-walled sections of the finished casting mold. The insulating effect of the hollow microspheres ensures that the metal in the thin-walled sections does not prematurely solidify and thus clog the paths within the casting mold.
  • the binder due to the low density of these hollow microspheres, is preferably used in a proportion in the range of preferably less than 20% by weight, particularly preferably in the range from 10 to 18% by weight.
  • the hollow microspheres are preferably made of an aluminum silicate. These aluminum silicate microbubbles preferably have an aluminum oxide content of more than 20% by weight, but may also have a content of more than 40% by weight.
  • Such hollow microspheres are, for example, from Omega Minerals Germany GmbH, Norderstedt, under the names OmegaSpheres® SG with an aluminum oxide content of about 28-33%, Omega-Spheres® WSG with an aluminum oxide content of about 35-39% and E-Spheres® with an aluminum oxide content of about 43% in the trade. Corresponding products are available from PQ Corporation (USA) under the name "Extendospheres®".
  • hollow microspheres are used as the refractory molding base, which are made of glass.
  • the hollow microspheres consist of a borosilicate glass.
  • the borosilicate glass has a proportion of boron, calculated as B 2 O 3 , of more than 3% by weight.
  • the proportion of hollow microspheres is preferably chosen to be less than 20% by weight, based on the molding material mixture.
  • a small proportion is preferably selected. This is preferably less than 5 wt .-%, preferably less than 3 wt .-%, and is more preferably in the range of 0.01 to 2 Gew. -%.
  • the molding material mixture according to the invention in a preferred embodiment contains at least a proportion of glass granules and / or glass beads as refractory molding base material.
  • the molding material mixture is an exothermic molding material mixture, which is suitable, for example, for the production of exothermic feeders.
  • the oxidizable metals preferably form a proportion of 15 to 35 wt .-%.
  • the oxidizing agent is preferably added in a proportion of 20 to 30 wt .-%, based on the molding material mixture.
  • Suitable oxidizable metals are, for example, aluminum or magnesium.
  • Suitable oxidizing agents are, for example, iron oxide or potassium nitrate.
  • the molding material mixture according to the invention contains a proportion of platelet-shaped lubricants, in particular graphite or MoS 2 .
  • platelet-shaped lubricants in particular graphite or MoS 2 .
  • the amount of added platelet-shaped lubricant, in particular graphite is preferably 0.1 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 separation of the molds from the mold. Suitable internal release agents are, for example, calcium stearate, fatty acid esters, waxes, natural resins or special alkyd resins.
  • silanes can also be added to the molding material mixture according to the invention.
  • the molding material mixture according to the invention contains an organic additive which has a melting point in the range from 40 to 180 ° C., preferably from 50 to 175 ° C., ie is solid at room temperature.
  • Organic additives are understood to be compounds whose molecular skeleton is composed predominantly of carbon atoms, that is, for example, organic polymers.
  • the quality of the surface of the casting can be further improved.
  • the mechanism of action of the organic additives has not been clarified. Without wishing to be bound by this theory, however, the inventors assume that at least some of the organic additives are burnt during the casting process, thereby creating a thin gas cushion between the liquid metal and the molding material forming the wall of the casting mold and thus a reaction between the liquid metal and the molding material is prevented. Further, the inventors believe that some of the organic additives under the reducing atmosphere of the casting form a thin layer of so-called lustrous carbon, which also prevents reaction between metal and molding material. As a further advantageous effect, an increase in the strength of the casting mold after curing can be achieved by adding the organic additives.
  • the organic additives are preferably used in an amount of 0.01 to 1.5% by weight, more preferably 0.05 to 1.3% by weight, particularly preferably 0.1 to 1.0% by weight, respectively based on the molding material added.
  • Suitable organic additives are, for example, phenol-formaldehyde resins, such as novolacs, epoxy resins, such as bisphenol A epoxy resins, bisphenol F epoxy resins or epoxidized novolacs, polyols, such as Polyethylene glycols or polypropylene glycols, polyolefins such as polyethylene or polypropylene, copolymers of olefins such as ethylene or propylene, and other comonomers such as vinyl acetate, polyamides such as polyamide-6, polyamide-12 or polyamide-6,6, natural resins such for example, gum rosin, fatty acid esters such as cetyl palmitate, fatty acid amides such as ethylenediamine bisstearamide, and metal soaps such as stearates or oleates of di- or tri-valent metals.
  • the organic additives can be contained both as
  • 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.
  • silanes examples include ⁇ -aminopropyltrimethoxysilane, ⁇ -hydroxypropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) trimethoxysilane and N- ⁇ (aminoethyl) - ⁇ -aminopropyltrimethoxysilane.
  • silane Based on the particulate metal oxide typically about 5 to 50% silane are used, preferably about 7 to 45%, more preferably about 10 to 40%.
  • the procedure is generally such that initially the refractory molding base material is introduced and then the binder is added with stirring.
  • the water glass as well as the particulate metal oxide, i. the synthetic amorphous silica may be added per se in any order.
  • 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.
  • the molding material mixture is then cured by supplying heat in order to evaporate the water contained in the binder.
  • the heating can be done for example in the mold. It is possible to fully cure the mold already in the mold. But it is also possible to cure the mold only in its edge region, so that it has sufficient strength to be removed from the mold can.
  • the casting mold can then be completely finished be cured by their further water is withdrawn. This can be done for example in an oven.
  • the dehydration can for example also be done by the water is evaporated at reduced pressure.
  • the curing of the molds is accelerated by blowing heated air into the mold.
  • a rapid removal of the water contained in the binder is achieved, whereby the mold is solidified in suitable periods for industrial use.
  • the temperature of the injected air is preferably 100 ° C to 180 ° C, particularly preferably 120 ° C to 150 ° C.
  • the flow rate of the heated air is preferably adjusted to cure the mold in periods suitable for industrial use. The periods depend on the size of the molds produced. It is desirable to cure in less than 5 minutes, preferably less than 2 minutes. For very large molds, however, longer periods may be required.
  • the removal of the water from the molding material mixture can also be carried out in such a way that the heating of the molding material mixture is effected by irradiation of microwaves.
  • the irradiation of the microwaves is preferably carried out after the casting mold has been removed from the molding tool.
  • the casting mold must already have sufficient strength. As already explained, this can be achieved, for example, by curing at least one outer shell of the casting mold already in the molding tool.
  • the flowability of the molding material mixture according to the invention can be improved by the addition of platelet-shaped lubricants, in particular graphite and / or MoS 2 .
  • the platy Lubricant, in particular graphite thereby be added separately from the two binder components of the molding material mixture.
  • the addition of the organic additive per se can be carried out at any 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 solvent. As such, solutions or pastes of the organic additives can also be prepared in organic solvents. However, if a solvent is used for the addition of the organic additives, water is preferably used.
  • the addition of the organic additives is carried out as a powder or as a short fiber, wherein the average particle size or the fiber length is preferably selected so that it does not exceed the size of the molding material particles.
  • the organic additives can be sieved through a sieve with the mesh size of about 0.3 mm.
  • the particulate Metal oxide and the organic or the additives preferably not separately added to the molding sand, but mixed in advance.
  • the silanes are usually added in the form that they are incorporated into the binder in advance.
  • the silanes can also be added to the molding material as a separate component.
  • it is particularly advantageous to silanize the particulate metal oxide i. To mix the metal oxide with the silane, so that its surface is provided with a thin silane layer. If one uses the thus pretreated particulate metal oxide, one finds compared to the untreated metal oxide increased strengths and an improved resistance to high humidity. If, as described, an organic additive is added to the molding material mixture or the particulate metal oxide, it is expedient to do so before the silanization.
  • the inventive method is in itself suitable for the production of all casting molds customary for metal casting, that is to say, for example, of cores and molds.
  • the inventive method for the production of feeders is.
  • the molds produced by the method according to the invention have a high strength immediately after production, without the strength of the molds after curing is so high that difficulties after the production of the casting during removal of the mold occur. Furthermore, these molds have a high stability at elevated humidity, ie the molds can be stored easily for a long time.
  • Another object of the invention is therefore a casting mold which has been obtained by the process according to the invention described above.
  • the casting mold produced by the process according to the invention is generally suitable for metal casting, in particular light metal casting. Particularly advantageous results are obtained in aluminum casting.
  • Georg Fischer test bars are cuboid test bars measuring 150 mm x 22.36 mm x 22.36 mm.
  • test bars were placed in a Georg Fischer strength testing machine equipped with a 3-point bending device (DISA Industrie AG, Schaffhausen, CH) and the force was measured which resulted in the breakage of the test bars.
  • Examples 1.4 to 1.7 increasing amounts of amorphous silica, which had been produced in the electric arc furnace, were added to the molding material mixtures. The amount of mold base and water glass was kept constant.
  • Comparative Example 1.1 a molding material mixture was prepared, which had the same composition as the molding material mixtures of Examples 1.4 to 1.7, but no amorphous silica was added.
  • the results from Table 2 show that the addition of amorphous, arc-prepared silica markedly increases the flexural strength of the test bars.
  • the flexural strength of the test bars increases particularly strongly in the case of a measurement after storage in the climatic cabinet at elevated air humidity. This means that the test bars produced with the molding material mixture according to the invention substantially retain their strength even after prolonged storage.
  • Increasing amounts of added amorphous silica lead to increasing flexural strengths.
  • the flexural strengths measured after storage in the climatic chamber, a strong increase in the flexural strengths is observed initially, which flattens out as the amount of added amorphous silicon dioxide increases.
  • Examples 1.4, 1.8 and 1.9 equal amounts of mold base, water glass and amorphous silicon dioxide (produced in the arc) were processed, but the ratio SiO 2 : M 2 O of the alkali water glass was changed.
  • the comparative examples 1.1, 1.2 and 1.3 in each case equal amounts of mold base material and water glass were processed, but also the ratio SiO 2 : M 2 O of the alkali water glass was varied.
  • the amorphous silica produced in the arc furnace is effective regardless of the ratio SiO 2 : M 2 O of the alkali water glass.
  • Examples 1.4, 1.10 and 1.11 equal amounts of mold base, water glass and amorphous silica were processed respectively, but the nature of the synthetic amorphous silica was varied.
  • the flexural strengths listed in Table 2 show that precipitated and pyrogenic, by Flame hydrolysis produced silicas are as effective as in the arc furnace produced amorphous silica.
  • the hot strengths and high humidity resistance can be improved without simultaneously increasing the cold strengths.
  • Examples 3.3-3.5 show that the addition of silane has a positive effect on the strengths, especially with respect to the resistance to high humidity.
  • the positive effect of the amorphous silica is not limited to quartz sand as a molding material, but that it also increases the strength of other molding materials, e.g. Microspheres, ceramic balls and glass beads.
  • composition was used as exothermic composition: Aluminum (0.063 - 0.5 mm grain size) 25% potassium nitrate 22% Hollow microspheres (Omegaspheres® WSG from Omega Minerals Germany GmbH) 44% Refractory surcharge (fireclay) 9%
  • the amorphous silica also increases strength in the case of exothermic compositions as a molding material.
  • the flowability of the molding material mixtures was determined by means of the degree of filling of the in Fig. 1 determined mold 1 determined.
  • the mold 1 consists of two halves, which can be connected to each other, so that a cavity 2 is formed.
  • the cavity 2 comprises three chambers 2a, 2b and 2c of circular cross-section having a diameter of 100 mm and a height of 30 mm.
  • the chambers 2a, 2b and 2c are each connected by circular openings 3a, 3b having a diameter of 15 mm.
  • the circular openings are made in partitions 4a, 4b, which have a thickness of 8 mm.
  • the openings 3a, 3b are each 37.5 mm to the central axis 6 offset at a maximum distance from each other.
  • an access 5 through which the molding material mixture can be filled.
  • the access 5 has a circular cross section with a diameter of 15 mm.
  • a vent opening 7 is further provided, which has a circular cross-section with a diameter of 9 mm and which is provided with a so-called slot nozzle.
  • the mold 1 is used for filling in a core shooting machine.
  • the determined weights of the moldings are summarized in Table 12.
  • Table 11 ⁇ / u> Composition of the molding material mixtures Quartz sand H 32 Alkali water glass a) amorphous silica b) graphite 6.1 100 GT 2.5 GT 0.2 GT - Comparison, not according to the invention 6.2 100 GT 2.5 GT 0.2 GT 0.2 GT inventively 6.3 100 GT 2.5 GT 0.2 GT 0.2 GT inventively 6.4 100 GT 2.5 GT 0.2 GT 1.0 GT inventively a) Alkali water glass with modulus SiO 2 : M 2 O of approx. 2.3 b) Elkem Microsilica 971 Weight of the moldings Weight [g] 6.1 512 Comparison, not according to the invention 6.2 534 inventively 6.3 564 inventively 6.4 588 inventively
  • Table 13 Composition of the molding material mixtures and casting result Composition see Ex. surface finish 7.1 1.1 (Tab. 1) 5 Comparison, not according to the invention 7.2 1.4 (Tab. 1) 5 inventively 7.3 4.1 (Tab. 7) 2 not according to the invention 7.4 4.2 (Tab. 7) 2 inventively 7.5 4.4 (Tab. 7) 4 not according to the invention 7.6 4.5 (Tab. 7) 4 inventively 7.7 4.6 (Tab. 7) 1 not according to the invention 7.8 4.7 (Tab. 7) 1 inventively
  • composition of the investigated molding material mixtures is listed in Table 14.
  • Table 14 shows that the addition of organic additives improves the casting surface.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Mold Materials And Core Materials (AREA)
  • Dental Prosthetics (AREA)
  • Molds, Cores, And Manufacturing Methods Thereof (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Lubricants (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)

Claims (21)

  1. Procédé de production de moules pour le travail des métaux, comprenant les étapes consistant à :
    - préparer un mélange de matières de moulage, comprenant au moins une matière de base de moulage résistant au feu ; un liant à base de verre soluble et une proportion d'un oxyde de métal particulaire, l'oxyde de métal particulaire étant un dioxyde de silicium amorphe préparé par synthèse ;
    - mettre en forme le mélange de matières de moulage,
    - durcir le mélange de matières de moulage, en chauffant le mélange de matières de moulage au moins par l'insufflation d'air chauffé, un moule durci étant ainsi obtenu.
  2. Procédé selon la revendication 1, dans lequel le mélange de matières de moulage est porté à une température située dans la plage de 100 à 300°C.
  3. Procédé selon la revendication 1 ou 2, dans lequel la température de l'air insufflé est située dans la plage de 100°C jusqu'à 180°C et de préférence 120°C à 150°C.
  4. Procédé selon au moins l'une des revendications précédentes, dans lequel la vitesse de circulation de l'air chauffé est réglée de sorte qu'un durcissement du moule s'effectue en une durée inférieure à 5 minutes, de préférence inférieure à 2 minutes.
  5. Procédé selon au moins l'une des revendications précédentes, dans lequel le moule est une forme, un noyau ou une masselotte.
  6. Procédé selon au moins l'une des revendications précédentes, caractérisé en ce que l'oxyde de métal particulaire est choisi dans le groupe constitué par la silice précipitée et la silice pyrogénée.
  7. Procédé selon au moins l'une des revendications précédentes, dans lequel le verre soluble présente un module SiO2/M2O situé dans la plage allant de 1,6 à 4,0, en particulier de 2,0 à 3,5, où M représente des ions sodium et/ou des ions potassium.
  8. Procédé selon au moins l'une des revendications précédentes, dans lequel le verre soluble présente une proportion de SiO2 et de M2O solides dans la plage de 30 à 60 % en poids.
  9. Procédé selon au moins l'une des revendications précédentes, dans lequel le liant est présent en une proportion inférieure à 20 % en poids dans le mélange de matières de moulage.
  10. Procédé selon au moins l'une des revendications précédentes, dans lequel l'oxyde de métal particulaire est présent en une proportion de 2 à 60 % en poids par rapport au liant.
  11. Procédé selon au moins l'une des revendications précédentes, dans lequel la matière de base de moulage comprend au moins une proportion de microsphères creuses et les microsphères creuses sont des microsphères creuses de silicate d'aluminium et/ou des microsphères creuses de verre.
  12. Procédé selon au moins l'une des revendications précédentes, dans lequel la matière de base de moulage comprend au moins une proportion de granulés de verre, de perles de verre et/ou de corps moulés céramiques sphériques.
  13. Procédé selon au moins l'une des revendications précédentes, dans lequel la matière de base de moulage comprend au moins une proportion de mullite, de sable de chromite et/ou d'olivine.
  14. Procédé selon au moins l'une des revendications précédentes, dans lequel le mélange de matières de moulage est additionné d'un métal oxydable ou d'un agent oxydant.
  15. Procédé selon au moins l'une des revendications précédentes, dans lequel le mélange de matières de moulage comprend une proportion d'un agent lubrifiant lamellaire et l'agent lubrifiant lamellaire est notamment choisi parmi le graphite et le sulfure de molybdène.
  16. Procédé selon au moins l'une des revendications précédentes, dans lequel le mélange de matières de moulage comprend une proportion d'au moins un additif organique solide à température ambiante.
  17. Procédé selon au moins l'une des revendications précédentes, dans lequel le mélange de matières de moulage comprend au moins un silane.
  18. Procédé selon au moins l'une des revendications précédentes, dans lequel la taille de particules des oxydes de métal particulaires est inférieure à 300 µm, de préférence inférieure à 200 µm et notamment inférieure à 100 µm.
  19. Procédé selon au moins l'une des revendications précédentes, dans lequel le mélange de matières de moulage est coulé au moyen d'une machine à tirer les noyaux à l'aide d'air comprimé dans l'outil de moulage, est durci par apport de chaleur, et le chauffage s'effectue dans l'outil de moulage.
  20. Moule obtenu selon un procédé selon l'une des revendications 1 à 19.
  21. Utilisation du moule selon la revendication 20 pour la coulée de métal, en particulier la coulée de métaux légers.
EP11006910.1A 2004-09-02 2005-09-02 Procédé de fabrication de moules pour le traitement du métal, moules fabriqués selon ce procédé et leur utilisation Active EP2392424B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PL11006910T PL2392424T3 (pl) 2004-09-02 2005-09-02 Sposób wytwarzania form odlewniczych do przetwarzania metali, formy odlewnicze wytworzone według tego sposobu i ich zastosowanie
SI200532269T SI2392424T1 (sl) 2004-09-02 2005-09-02 Postopek za izdelavo livarskih kalupov za obdelavo kovin, livarski kalupi, izdelani po tem postopku, in njihova uporaba

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102004042535.3A DE102004042535B4 (de) 2004-09-02 2004-09-02 Formstoffmischung zur Herstellung von Gießformen für die Metallverarbeitung, Verfahren und Verwendung
PCT/EP2005/009470 WO2006024540A2 (fr) 2004-09-02 2005-09-02 Melange de matieres de moulage pour produire des moules pour le travail des metaux
EP05783967A EP1802409B1 (fr) 2004-09-02 2005-09-02 Melange de matieres de moulage pour produire des moules pour le travail des metaux

Related Parent Applications (2)

Application Number Title Priority Date Filing Date
EP05783967.2 Division 2005-09-02
EP05783967A Division EP1802409B1 (fr) 2004-09-02 2005-09-02 Melange de matieres de moulage pour produire des moules pour le travail des metaux

Publications (2)

Publication Number Publication Date
EP2392424A1 EP2392424A1 (fr) 2011-12-07
EP2392424B1 true EP2392424B1 (fr) 2019-11-06

Family

ID=35701554

Family Applications (2)

Application Number Title Priority Date Filing Date
EP05783967A Revoked EP1802409B1 (fr) 2004-09-02 2005-09-02 Melange de matieres de moulage pour produire des moules pour le travail des metaux
EP11006910.1A Active EP2392424B1 (fr) 2004-09-02 2005-09-02 Procédé de fabrication de moules pour le traitement du métal, moules fabriqués selon ce procédé et leur utilisation

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP05783967A Revoked EP1802409B1 (fr) 2004-09-02 2005-09-02 Melange de matieres de moulage pour produire des moules pour le travail des metaux

Country Status (23)

Country Link
US (1) US7770629B2 (fr)
EP (2) EP1802409B1 (fr)
JP (1) JP5102619B2 (fr)
KR (1) KR101301829B1 (fr)
CN (1) CN100563869C (fr)
AT (1) ATE542619T1 (fr)
AU (1) AU2005279301A1 (fr)
BR (1) BRPI0514810A (fr)
CA (1) CA2578437C (fr)
DE (2) DE102004042535B4 (fr)
DK (1) DK1802409T3 (fr)
ES (2) ES2769603T3 (fr)
HR (1) HRP20120325T1 (fr)
HU (1) HUE047434T2 (fr)
IL (1) IL181594A0 (fr)
MX (1) MX2007002585A (fr)
NO (1) NO20071755L (fr)
PL (2) PL2392424T3 (fr)
PT (1) PT1802409E (fr)
RU (1) RU2007111891A (fr)
SI (2) SI2392424T1 (fr)
WO (1) WO2006024540A2 (fr)
ZA (1) ZA200701859B (fr)

Families Citing this family (77)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005041863A1 (de) * 2005-09-02 2007-03-29 Ashland-Südchemie-Kernfest GmbH Borsilikatglashaltige Formstoffmischungen
DE102006011530A1 (de) 2006-03-10 2007-09-13 Minelco Gmbh Form oder Formling, Gießerei-Formstoffgemisch und Verfahren zu seiner Herstellung
FR2902424B1 (fr) * 2006-06-19 2008-10-17 Saint Gobain Ct Recherches Ciment de jointoiement a spheres creuses pour filtre a particules.
DE102006036381A1 (de) * 2006-08-02 2008-02-07 Minelco Gmbh Formstoff, Gießerei-Formstoff-Gemisch und Verfahren zur Herstellung einer Form oder eines Formlings
EP2104580B2 (fr) * 2006-10-19 2022-02-23 ASK Chemicals GmbH Mélange de matières de moulage à base d'hydrates de carbone
DE102006049379A1 (de) * 2006-10-19 2008-04-24 Ashland-Südchemie-Kernfest GmbH Phosphorhaltige Formstoffmischung zur Herstellung von Giessformen für die Metallverarbeitung
CN101626854B (zh) * 2007-01-29 2012-07-04 赢创德固赛有限责任公司 用于熔模铸造的热解金属氧化物
DE102007008149A1 (de) * 2007-02-19 2008-08-21 Ashland-Südchemie-Kernfest GmbH Thermische Regenerierung von Gießereisand
DE102007009468A1 (de) * 2007-02-27 2008-08-28 Mtu Aero Engines Gmbh Verfahren zur Herstellung eines Strukturelements
DE102007012660B4 (de) * 2007-03-16 2009-09-24 Chemex Gmbh Kern-Hülle-Partikel zur Verwendung als Füllstoff für Speisermassen
DE102007026229A1 (de) * 2007-06-05 2008-12-11 Bayerische Motoren Werke Aktiengesellschaft Verfahren zur Herstellung eines Strukturhohlbauteils aus faserverstärktem Kunststoff
DE102007027577A1 (de) 2007-06-12 2008-12-18 Minelco Gmbh Formstoffmischung, Formling für Gießereizwecke und Verfahren zur Herstellung eines Formlings
DE102007045649B4 (de) 2007-09-25 2015-11-19 H2K Minerals Gmbh Verfahren zur Herstellung einer Form und/oder eines Kernes unter Verwendung von zerkleinerten natürlichen partikulären amorphen Kieselsäurematerialien im Gießereibereich und Binderzusammensetzung
DE102007051850A1 (de) * 2007-10-30 2009-05-07 Ashland-Südchemie-Kernfest GmbH Formstoffmischung mit verbesserter Fliessfähigkeit
DE102007061968A1 (de) 2007-12-21 2009-06-25 Ashland-Südchemie-Kernfest GmbH Haltbare Beschichtungen für Werkzeuge zur Herstellung von Kernen, Formen und Speisern für den Metallguss
FR2948307B1 (fr) * 2009-07-24 2014-07-25 Huettenes Albertus France Procede d'obtention d'un corps forme a partir d'un melange granulaire
KR101199111B1 (ko) * 2009-10-30 2012-11-09 현대자동차주식회사 주물용 중자 재료 혼합물, 주물용 중자 제조방법 및 이를 이용하여 제조된 주물용 중자
KR101273962B1 (ko) * 2010-12-21 2013-06-12 재단법인 포항산업과학연구원 쌍롤식 박판주조기용 에지댐
UA106559C2 (uk) * 2010-12-30 2014-09-10 Аск Кемикалз Эспанья, С.А. Протижилкувальна домішка для виготовлення ливарних форм або стержнів
DE102011102454A1 (de) * 2011-05-24 2012-11-29 Bernd Kuhs Anorganisches Bindemittel und Verfahren zur schnellen Verfestigung von Baustoffmaterialien aller Art mittels Begasung mit Kohlendioxid
DE102011114626A1 (de) 2011-09-30 2013-04-04 Ask Chemicals Gmbh Beschichtungsmassen für anorganische Giessformen und Kerne und deren Verwendung
DE102011115024A1 (de) 2011-10-07 2013-04-11 Ask Chemicals Gmbh Beschichtungsmassen für anorganische Gießformen und Kerne umfassend Ameisensäureester und deren Verwendung
DE102011115025A1 (de) 2011-10-07 2013-04-11 Ask Chemicals Gmbh Beschichtungsmassen für anorganische Gießformen und Kerne enthaltend Salze und deren Verwendung
JP4920794B1 (ja) * 2011-11-02 2012-04-18 株式会社ツチヨシ産業 鋳型材料及び鋳型並びに鋳型の製造方法
DE102012103705A1 (de) 2012-04-26 2013-10-31 Ask Chemicals Gmbh Verfahren zur Herstellung von Formen und Kernen für den Metallguss sowie nach diesem Verfahren hergestellte Formen und Kerne
DE102012104934A1 (de) 2012-06-06 2013-12-12 Ask Chemicals Gmbh Forstoffmischungen enthaltend Bariumsulfat
DE102012020511A1 (de) 2012-10-19 2014-04-24 Ask Chemicals Gmbh Formstoffmischungen auf der Basis anorganischer Bindemittel und Verfahren zur Herstellung von Formen und Kerne für den Metallguss
DE102012020509A1 (de) 2012-10-19 2014-06-12 Ask Chemicals Gmbh Formstoffmischungen auf der Basis anorganischer Bindemittel und Verfahren zur Herstellung von Formen und Kerne für den Metallguss
DE102012020510B4 (de) 2012-10-19 2019-02-14 Ask Chemicals Gmbh Formstoffmischungen auf der Basis anorganischer Bindemittel und Verfahren zur Herstellung von Formen und Kerne für den Metallguss
CN102921885B (zh) * 2012-10-30 2015-01-28 西安泵阀总厂有限公司 钛、锆、镍及其合金铸件砂型铸造工艺
DE102012113073A1 (de) * 2012-12-22 2014-07-10 Ask Chemicals Gmbh Formstoffmischungen enthaltend Aluminiumoxide und/oder Aluminium/Silizium-Mischoxide in partikulärer Form
DE102012113074A1 (de) * 2012-12-22 2014-07-10 Ask Chemicals Gmbh Formstoffmischungen enthaltend Metalloxide des Aluminiums und Zirkoniums in partikulärer Form
US20150367406A1 (en) 2013-01-04 2015-12-24 S & B Industrial Minerals Gmbh Method for the production of core sand and/or molding sand for casting purposes
DE102013106276A1 (de) 2013-06-17 2014-12-18 Ask Chemicals Gmbh Lithiumhaltige Formstoffmischungen auf der Basis eines anorganischen Bindemittels zur Herstellung von Formen und Kernen für den Metallguss
CN103302231A (zh) * 2013-06-20 2013-09-18 重庆长江造型材料（集团）股份有限公司 一种水基型粘结剂湿态型芯的固化方法
US20150078912A1 (en) * 2013-09-18 2015-03-19 General Electric Company Ceramic core compositions, methods for making cores, methods for casting hollow titanium-containing articles, and hollow titanium-containing articles
CN103567364A (zh) * 2013-10-11 2014-02-12 铜陵市经纬流体科技有限公司 用于铸铝的型砂及其制备方法
ES2628255T3 (es) 2013-10-19 2017-08-02 Peak Deutschland Gmbh Procedimiento para producir machos perdidos o piezas de molde para la producción de piezas fundidas.
DE102013111626A1 (de) * 2013-10-22 2015-04-23 Ask Chemicals Gmbh Formstoffmischungen enthaltend eine oxidische Bor-Verbindung und Verfahren zur Herstellung von Formen und Kernen
DE102013114581A1 (de) 2013-12-19 2015-06-25 Ask Chemicals Gmbh Verfahren zur Herstellung von Formen und Kernen für den Metallguss unter Verwendung einer Carbonylverbindung sowie nach diesem Verfahren hergestellte Formen und Kerne
DE102014106177A1 (de) * 2014-05-02 2015-11-05 Ask Chemicals Gmbh Formstoffmischung enthaltend Resole und amorphes Siliciumdioxid, aus diesen hergestellte Formen und Kerne und Verfahren zu deren Herstellung
CN104014715B (zh) * 2014-05-29 2016-04-13 朱小英 一种铝合金铸造型砂的制备方法
CN106660109B (zh) 2014-06-20 2019-11-19 旭有机材株式会社 铸型的制造方法和铸型
CN104439041A (zh) * 2014-10-20 2015-03-25 沈阳汇亚通铸造材料有限责任公司 一种温芯盒制芯砂组合物及制芯方法
DE102014118577A1 (de) 2014-12-12 2016-06-16 Ask Chemicals Gmbh Verfahren zum schichtweisen Aufbau von Formen und Kernen mit einem wasserglashaltigen Bindemittel und ein wasserglashaltiges Bindemittel
KR101527909B1 (ko) * 2014-12-16 2015-06-10 한국생산기술연구원 주조용 무기 바인더 조성물
KR101614401B1 (ko) 2015-03-10 2016-04-21 (주)피알테크 주물사용 무기 바인더 조성물
DE102015223008A1 (de) 2015-11-21 2017-05-24 H2K Minerals Gmbh Form, Verfahren zu ihrer Herstellung und Verwendung
CN108778557B (zh) * 2015-12-18 2020-03-06 亚世科化学有限责任公司 用于非铁金属铸造的造型材料
CN105665615B (zh) * 2016-02-05 2018-10-02 济南圣泉集团股份有限公司 一种铸造水玻璃用固化剂及其制备方法和用途
ITUA20162227A1 (it) 2016-04-01 2017-10-01 Cavenaghi S P A Sistema legante inorganico per fonderia
US20180056373A1 (en) 2016-08-29 2018-03-01 Charles Earl Bates Anti-Veining Additive for Silica Sand Mold
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
EA201991683A1 (ru) * 2017-01-11 2019-12-30 Дуглас М. Триновски Композиции и способы для литейных стержней при литье под высоким давлением
CN108393430B (zh) 2017-02-04 2020-05-08 济南圣泉集团股份有限公司 一种铸造水玻璃用固化剂
DE102017107531A1 (de) 2017-04-07 2018-10-11 HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung Verfahren zur Herstellung von Gießformen, Kernen und daraus regenerierten Formgrundstoffen
DE102017114628A1 (de) 2017-06-30 2019-01-03 HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung Verfahren zur Herstellung einer Formstoffmischung und eines Formkörpers daraus in der Gießereiindustrie sowie Kit zur Anwendung in diesem Verfahren
JP6888527B2 (ja) 2017-11-09 2021-06-16 新東工業株式会社 鋳型用発泡骨材混合物、鋳型、及び鋳型の製造方法
EP3501690A1 (fr) 2017-12-20 2019-06-26 Imertech Sas Procédé de fabrication d'articles de fonderie de matériau réfractaire a base de particules, et produit fabriqué par ce procédé
CN111511483B (zh) 2017-12-28 2021-08-03 旭有机材株式会社 覆膜砂和其制造方法以及铸型的制造方法
WO2019132007A1 (fr) 2017-12-28 2019-07-04 旭有機材株式会社 Matériau de moule de coulée, procédé de production pour matériau de moule de coulée, et procédé de production pour moule de coulée
ES2883555T3 (es) 2018-09-07 2021-12-09 Huettenes Albertus Chemische Werke Gmbh Método para preparar una composición refractaria en partículas para su uso en la producción de moldes y machos de fundición, usos correspondientes y mezcla de recuperación para tratamiento térmico
DE102019113008A1 (de) 2019-05-16 2020-11-19 HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung Verwendung eines partikulären Materials umfassend ein teilchenförmiges synthetisches amorphes Siliciumdioxid als Additiv für eine Formstoffmischung, entsprechende Verfahren, Mischungen und Kits
CN110064727A (zh) * 2019-06-10 2019-07-30 沈阳汇亚通铸造材料有限责任公司 一种酯固化铸造用水玻璃砂组合物
DE102019116406A1 (de) 2019-06-17 2020-12-17 HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung Additivmischung für Formstoffmischungen zur Herstellung wasserglasgebundener Gießereiformen und Gießereikerne
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
DE102019131241A1 (de) 2019-08-08 2021-02-11 HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung Verfahren zur Herstellung eines Artikels zur Verwendung in der Gießereiindustrie, entsprechendes Granulat sowie Kit, Vorrichtungen und Verwendungen
DE102020110289A1 (de) * 2020-04-15 2021-10-21 Peak Deutschland Gmbh Verfahren unter Verwendung eines anorganischen Binders für die Herstellung von ausgehärteten dreidimensional geschichteten Formkörpern für Gießereikerne und -formen
DE102020119013A1 (de) 2020-07-17 2022-01-20 HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung Verfahren zur Herstellung eines Artikels zur Verwendung in der Gießereiindustrie, entsprechende Form, Kern, Speiserelement oder Formstoffmischung sowie Vorrichtungen und Verwendungen
CN112028596B (zh) * 2020-09-01 2022-04-08 和县华顺铸造有限公司 一种铸造封箱泥膏的制备方法
CN112264575B (zh) * 2020-10-20 2021-11-19 西安工程大学 一种模具摇摆法空心陶瓷型芯及其制备方法
DE102020127603A1 (de) 2020-10-20 2022-04-21 Kurtz Gmbh Verfahren und Vorrichtung zum Gießen eines metallenen Gussteils mittels eines Sandkernes
EP4286072A1 (fr) * 2021-01-29 2023-12-06 Kao Corporation Sable enduit inorganique
DE102021116930A1 (de) 2021-06-30 2023-01-05 Ask Chemicals Gmbh Verfahren zum schichtweisen aufbau von formen und kernen mit einem wasserglashaltigen bindemittel
EP4370263A1 (fr) * 2021-07-12 2024-05-22 Foseco International Limited Système de liants inorganiques

Family Cites Families (42)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2881081A (en) * 1954-06-02 1959-04-07 John A Henricks Refractory binder for metal casting molds
GB782205A (en) 1955-03-07 1957-09-04 Foundry Services Ltd Improvements in or relating to sand cores
US3429848A (en) 1966-08-01 1969-02-25 Ashland Oil Inc Foundry binder composition comprising benzylic ether resin,polyisocyanate,and tertiary amine
FR2237705A1 (en) * 1973-07-17 1975-02-14 Du Pont Sand core or mould for metal casting - prepd. by shaping and hardening silicon oxide sand-alkali silicate mixture
IT1017203B (it) * 1973-07-17 1977-07-20 Du Pont Legane per terra da fonderia a base di silicati ad elevato rap porto silice ossido di metallo alcalino
US4162238A (en) 1973-07-17 1979-07-24 E. I. Du Pont De Nemours And Company Foundry mold or core compositions and method
US4316744A (en) 1973-07-17 1982-02-23 E. I. Du Pont De Nemours And Company High ratio silicate foundry sand binders
JPS52810B2 (fr) * 1973-11-07 1977-01-11
JPS5135621A (ja) * 1974-09-20 1976-03-26 Nippon Steel Corp Jikoseiigatanoseizoho
JPS5149121A (en) * 1974-10-25 1976-04-28 Hitachi Ltd Igatano setsuchakuzai
JPS52124414A (en) * 1976-04-14 1977-10-19 Kogyo Gijutsuin Molding material
JPS52138434A (en) * 1976-05-14 1977-11-18 Toyo Kogyo Co Self harden molding material
JPS52146720A (en) * 1976-05-31 1977-12-06 Toyo Kogyo Co Water glass system binding material for mold
AT381884B (de) * 1979-03-14 1986-12-10 Brugger Gottfried Schlichte fuer die herstellung einer auskleidung von metallischen schleudergusskokillen fuer kupfer oder dessen legierungen und verfahren zur beschichtung einer schleudergusskokille
JPS57127074A (en) * 1981-01-30 1982-08-07 Mitsubishi Heavy Ind Ltd Construction of concrete liquid tank
JPS6171152A (ja) * 1984-09-13 1986-04-12 Komatsu Ltd 鋳型の製造方法
DE3600956A1 (de) * 1986-01-15 1987-07-16 Kuepper August Gmbh & Co Kg Verfahren zur herstellung von giessereikernen
US5275114A (en) * 1989-04-11 1994-01-04 American Colloid Company Sodium bentonite clay binder mixture for the metal casting industry
JPH0663683A (ja) * 1992-08-18 1994-03-08 Mitsubishi Heavy Ind Ltd 鋳型の製造方法
GB9226815D0 (en) 1992-12-23 1993-02-17 Borden Uk Ltd Improvements in or relating to water dispersible moulds
DE9307468U1 (de) * 1993-05-17 1994-09-29 Huettenes Albertus Schlichte zur Herstellung von Formüberzügen
US5382289A (en) 1993-09-17 1995-01-17 Ashland Oil, Inc. Inorganic foundry binder systems and their uses
US5417751A (en) 1993-10-27 1995-05-23 Ashland Oil, Inc. Heat cured foundry binders and their use
US5474606A (en) 1994-03-25 1995-12-12 Ashland Inc. Heat curable foundry binder systems
JPH07303935A (ja) * 1994-05-12 1995-11-21 Asahi Tec Corp 鋳型成形方法
US6139619A (en) * 1996-02-29 2000-10-31 Borden Chemical, Inc. Binders for cores and molds
DE19632293C2 (de) 1996-08-09 1999-06-10 Thomas Prof Dr In Steinhaeuser Verfahren zur Herstellung von Kernformlingen für die Gießereitechnik
US5837047A (en) 1996-12-11 1998-11-17 Ashland Inc. Heat curable binder systems and their use
AT2581U1 (de) * 1998-03-20 1999-01-25 Kaerntner Montanindustrie Ges Verwendung von eisenglimmer bei der herstellung von gussformen
JP3374242B2 (ja) * 1998-10-09 2003-02-04 正光 三木 鋳物用発熱性アセンブリ
DE19923779A1 (de) * 1999-05-22 2000-11-23 Luengen Gmbh & Co Kg As Formstoff für Brechkerne für den Sphäroguß
DE19925167A1 (de) 1999-06-01 2000-12-14 Luengen Gmbh & Co Kg As Exotherme Speisermasse
WO2001015833A2 (fr) * 1999-08-31 2001-03-08 Ashland Inc. Melanges pour manchons exothermiques contenant de l'aluminium fin
US6232368B1 (en) * 1999-10-12 2001-05-15 Borden Chemical, Inc. Ester cured binders
DE29925011U1 (de) 1999-10-26 2008-10-02 Minelco Gmbh Giessereikern-Bindemittelsystem
US6416572B1 (en) 1999-12-02 2002-07-09 Foseco International Limited Binder compositions for bonding particulate material
GB0026902D0 (en) 2000-11-03 2000-12-20 Foseco Int Machinable body and casting process
DE10145417A1 (de) * 2001-09-14 2003-05-22 Vaw Mandl & Berger Gmbh Linz Formgrundstoff, Formstoff und Formteil für eine Giessform
JP4149697B2 (ja) * 2001-11-02 2008-09-10 旭有機材工業株式会社 鋳型用有機粘結剤組成物及びそれを用いて成る鋳型用材料
CN1255234C (zh) * 2001-11-21 2006-05-10 沈阳汇亚通铸造材料有限责任公司 一种吹气硬化冷芯盒制芯的方法
DE10256953A1 (de) * 2002-12-05 2004-06-24 Ashland-Südchemie-Kernfest GmbH Heißhärtendes Bindemittel auf Polyurethanbasis
JP2005021962A (ja) * 2003-07-02 2005-01-27 Sintokogio Ltd 鋳型製造方法、その鋳型およびその鋳物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
BRPI0514810A (pt) 2008-06-24
JP5102619B2 (ja) 2012-12-19
DE102004042535B4 (de) 2019-05-29
US20080099180A1 (en) 2008-05-01
HRP20120325T1 (hr) 2012-05-31
JP2008511447A (ja) 2008-04-17
AU2005279301A1 (en) 2006-03-09
KR20070057233A (ko) 2007-06-04
IL181594A0 (en) 2007-07-04
PT1802409E (pt) 2012-05-08
KR101301829B1 (ko) 2013-08-30
DE202005021896U1 (de) 2011-01-20
CA2578437C (fr) 2013-01-29
NO20071755L (no) 2007-05-21
ATE542619T1 (de) 2012-02-15
EP2392424A1 (fr) 2011-12-07
EP1802409B1 (fr) 2012-01-25
DE102004042535A1 (de) 2006-03-09
SI2392424T1 (sl) 2020-03-31
WO2006024540A3 (fr) 2006-07-13
MX2007002585A (es) 2007-07-13
ZA200701859B (en) 2008-07-30
SI1802409T1 (sl) 2012-05-31
EP1802409A2 (fr) 2007-07-04
PL1802409T3 (pl) 2012-07-31
ES2769603T3 (es) 2020-06-26
US7770629B2 (en) 2010-08-10
CA2578437A1 (fr) 2006-03-09
CN100563869C (zh) 2009-12-02
ES2380349T3 (es) 2012-05-10
RU2007111891A (ru) 2008-10-10
PL2392424T3 (pl) 2020-05-18
DK1802409T3 (da) 2012-04-16
WO2006024540A2 (fr) 2006-03-09
CN101027147A (zh) 2007-08-29
HUE047434T2 (hu) 2020-04-28

Similar Documents

Publication Publication Date Title
EP2392424B1 (fr) Procédé de fabrication de moules pour le traitement du métal, moules fabriqués selon ce procédé et leur utilisation
EP2097192B1 (fr) Mélange de matières de moulage à base de phosphore, utilisé pour produire des moules pour la transformation de métaux
EP2104580B1 (fr) Mélange de matières de moulage à base d'hydrates de carbone
EP2209572B1 (fr) Mélange de matériaux de moulage de fluidité améliorée
DE102012020510B4 (de) Formstoffmischungen auf der Basis anorganischer Bindemittel und Verfahren zur Herstellung von Formen und Kerne für den Metallguss
EP2117749B1 (fr) Régénération thermique de sable de fonderie
EP2908968B1 (fr) Mélanges de matière à mouler à base de liant inorganique et procédé de production de moules et de noyaux pour la coulée de métaux
DE102012103705A1 (de) Verfahren zur Herstellung von Formen und Kernen für den Metallguss sowie nach diesem Verfahren hergestellte Formen und Kerne
DE102012020511A1 (de) Formstoffmischungen auf der Basis anorganischer Bindemittel und Verfahren zur Herstellung von Formen und Kerne für den Metallguss
DE102018200607A1 (de) Verfahren zur Erzeugung von für die Herstellung von Faserverbundkörpern oder Gussteilen aus Metall oder Kunststoff geeigneten Formen und Kernen, bei dem Verfahren einsetzbare Formgrundstoffe und Binder sowie gemäß dem Verfahren hergestellte Formen und Kerne
EP3137245B1 (fr) Mélanges de matériaux de moulage contenant des résols et du dioxyde de silicium amorphe, moules et noyaux fabriqués à partir de ces mélanges et procédé pour les fabriquer
EP3986634A1 (fr) Moules de fonderie poteyés pouvant être obtenus à partir d'un mélange de matières à mouler contenant un liant inorganique et des composés phosphatés et des composés d'oxyde de bore et procédé pour les fabriquer et leur utilisation
DE102006061876A1 (de) Kohlenhydrathaltige Formstoffmischung

Legal Events

Date Code Title Description
17P Request for examination filed

Effective date: 20110824

AC Divisional application: reference to earlier application

Ref document number: 1802409

Country of ref document: EP

Kind code of ref document: P

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: HR YU

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20180424

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: ASK CHEMICALS GMBH

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20190516

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AC Divisional application: reference to earlier application

Ref document number: 1802409

Country of ref document: EP

Kind code of ref document: P

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

Ref country code: AT

Ref legal event code: REF

Ref document number: 1198068

Country of ref document: AT

Kind code of ref document: T

Effective date: 20191115

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502005016095

Country of ref document: DE

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: TROESCH SCHEIDEGGER WERNER AG, CH

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: HU

Ref legal event code: AG4A

Ref document number: E047434

Country of ref document: HU

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191106

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200207

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200206

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191106

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191106

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200306

REG Reference to a national code

Ref country code: SK

Ref legal event code: T3

Ref document number: E 33416

Country of ref document: SK

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200306

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2769603

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20200626

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191106

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191106

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191106

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502005016095

Country of ref document: DE

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20200807

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SI

Payment date: 20200821

Year of fee payment: 16

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20201130

Year of fee payment: 16

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191106

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200902

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200902

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20210930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191106

REG Reference to a national code

Ref country code: SI

Ref legal event code: KO00

Effective date: 20220520

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210930

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230517

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: TR

Payment date: 20230828

Year of fee payment: 19

Ref country code: NL

Payment date: 20230920

Year of fee payment: 19

Ref country code: GB

Payment date: 20230921

Year of fee payment: 19

Ref country code: CZ

Payment date: 20230818

Year of fee payment: 19

Ref country code: AT

Payment date: 20230915

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SK

Payment date: 20230821

Year of fee payment: 19

Ref country code: SE

Payment date: 20230921

Year of fee payment: 19

Ref country code: PL

Payment date: 20230710

Year of fee payment: 19

Ref country code: HU

Payment date: 20230825

Year of fee payment: 19

Ref country code: FR

Payment date: 20230919

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20231019

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20230929

Year of fee payment: 19

Ref country code: DE

Payment date: 20231127

Year of fee payment: 19

Ref country code: CH

Payment date: 20231001

Year of fee payment: 19