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    • 专利摘要:
    The invention relates to mixtures of molding material containing a base molding material, water glass, amorphous silicon dioxide and an oxide boron compound, and the production of molds and cores, in particular for metal casting.
    公开号:BR112016008892B1
    申请号:R112016008892-1
    申请日:2014-10-21
    公开日:2021-01-12
    发明作者:Heinz Deters；Martin Oberleiter；Henning Zupan
    申请人:Ask Chemicals Gmbh；
    IPC主号:
    专利说明:

    [001] The invention relates to mixtures of molding material for the foundry industry, containing one or more oxide boron powder compounds in combination with refractory mold base materials, a binder system based on water and dioxide glass of amorphous particulate silicon, especially to produce aluminum molded parts, and a method for producing molds and casting cores from molding material mixtures that break easily after metal casting. Prior Art
    [002] Foundry molds are essentially made up of cores and molds that represent the negative shapes of the molded parts to be produced. These cores and molds consist of a refractory material, for example, quartz sand, and a suitable binder, which provides adequate mechanical strength to the casting mold after it is removed from the molding tool. Thus, to produce foundry molds, a base material of the refractory mold surrounded by a suitable binder is used. The base material of the refractory mold preferably exists in a fluid form, so that it can be filled into a suitable empty mold and compacted therein. The binder produces firm cohesion between the particles of the mold base material, so that the casting mold acquires the necessary mechanical stability.
    [003] Foundry molds have to meet several requirements. During the actual casting process, they must first have adequate mechanical strength and thermal resistance to retain the liquid metal in a cavity formed from one or more (partial) casting molds. After the solidification process begins, the mechanical stability of the casting is guaranteed by a solidified layer of metal that forms along the walls of the casting mold. The casting mold material now has to disappear due to the influence of the heat released by the metal when it loses its mechanical resistance, thus abolishing the cohesion between individual particles of the refractory material. Ideally, the casting mold disintegrates into fine sand, which can be effortlessly removed from the casting.
    [004] Furthermore, recently it has been demanded with increasing frequency that as far as possible emissions should not be produced in the form of CO2 or hydrocarbons during the production and cooling of the casting in order to protect the environment and limit the annoyance of odor to the area in the surroundings because of hydrocarbons, mainly aromatic hydrocarbons. To meet these requirements, in the past, inorganic binder systems have been developed, or additionally developed, the use of which means that CO2 and hydrocarbon emissions during the manufacture of metal molds can be avoided or at least distinctly reduced. However, the use of inorganic binder systems is often associated with other drawbacks, which will be described in detail in the following statements.
    [005] Compared with organic binders, inorganic binders have the drawback that the foundry molds prepared with them have relatively low strengths. This is in particular clearly apparent after removing the casting mold from the molding tool. However, good strength at this point in time is especially important for the production of more complicated moldings and / or thinner walls and their safe handling. Moisture resistance is also distinctly lower compared to organic binders.
    [006] EP 1802409 B1 describes that greater immediate resistance and greater resistance to atmospheric humidity can be conceived by the use of a refractory molding material, a binder based on water glass and the addition of particulate amorphous silicon dioxide. Through this use, safe handling of even complicated casting molds is guaranteed.
    [007] Inorganic binder systems also have the drawback, compared with organic binder systems, that the demoulding behavior, that is, the ability of the casting mold to break quickly (under mechanical stress) after the melting of the metal in a fluid form is often inferior in the case of casting molds made of pure inorganic material (for example, those using water glass as the binder) than in the case of casting molds produced with an organic binder.
    [008] This characteristic mentioned last, worse demolding behavior, is especially disadvantageous if thin, delicate or complex wall casting molds are used; theoretically, these would be difficult to remove after the second casting. An example that can be mentioned is the so-called water jacket males that are necessary in the manufacture of certain areas of an internal combustion engine.
    [009] Attempts have been made to add organic components to the molding material mixtures that would pyrolyze / react by the influence of the hot metal and thus facilitate the disintegration of the casting mold after casting by pore formation. An example of this is DE 2059538 (= GB 1299779 A). However, the amounts of glucose syrup added here are very large and are thus associated with considerable emission of CO2 and other pyrolysis products. Prior Technology Issues and Problem Statement
    [0010] The previously known inorganic binder systems for casting purposes still have an environment for improvement. In particular, it is desirable to develop an inorganic binder system that: a) allows the formation of a distinctly reduced amount of CO2 emissions and organic pyrolysis products, or no emissions (in the form of gases and / or aerosols, for example, aromatic hydrocarbons, fumes) during metal casting, b) it reaches an appropriate resistance level that is necessary in the automated manufacturing process (especially hot resistances and resistances after storage), c) it makes possible very good surface quality of the cast in question, so that at most little or no post-processing is required, and e) leads to very good disintegration of the casting mold after metal casting, so that the casting in question can be separated from the workpiece cast in question easily and residue-free.
    [0011] Thus, the invention was, therefore, based on the problem of providing a mixture of molding material to produce foundry molds for metal processing, which in particular effectively improves the disintegration properties of the foundry mold after metal casting. and at the same time it reaches the level of resistance that is required in the automated manufacturing process.
    [0012] Furthermore, the production of complex geometry casting molds must be enabled, which, for example, can also contain thin-walled sections. The casting mold must also have high storage stability and remain stable even at higher temperatures and humidity. Summary of the Invention
    [0013] The problems exposed will be solved by mixing molding material, the multicomponent system and / or the method with the resources of the independent claims. Advantageous additional embodiments of the molding material mixture according to the invention form the subject matter of the dependent claims or are described below.
    [0014] Surprisingly it was observed that, by adding one or more oxide-type boron compounds to the molding material mixture, foundry molds can be produced based on inorganic binders that have high strength immediately after production and after of extended storage.
    [0015] A decisive advantage is attributed to the fact that the addition of powdered borates leads to clearly improved disintegration properties of the casting mold after metal casting. This advantage is associated with distinctly lower costs to manufacture a casting, especially in the case of molded parts that have complex geometry with very small cavities, from which the casting mold has to be removed.
    [0016] According to one embodiment of the invention, the molding material mixture contains organic components in a maximum amount of 0.49% by weight, especially up to a maximum of 0.19% by weight, so that only very small amounts small CO2 emissions and other pyrolysis products are formed.
    [0017] For this reason, exposure to emissions hazardous to health in the workplace for workers employed in it and for people living in the area can be reduced. The use of the molding material mixture according to the invention also contributes to reducing emissions of CO2 and other organic pyrolysis products that are harmful to the climate.
    [0018] The molding material mixture to produce foundry molds for metal processing comprises at least: a base material of the refractory mold; and a water glass-based binder; and particulate amorphous silicon dioxide; and one or more powdered boron oxide compound (s). Detailed Description of the Invention
    [0019] Common known materials can be used as the base material of the refractory mold to produce foundry molds. Suitable, for example, are quartz, zirconia or chromite sand, olivine, vermiculite, bauxite, refractory clay and synthetic base mold materials, especially more than 50% by weight of quartz sand based on the base material of the refractory mold. It is not necessary here to use fresh sand exclusively here. In order to conserve resources and avoid disposal costs, it is still advantageous to use the highest possible fraction of regenerated used sand, such as that obtained from molds used for recycling.
    [0020] A base material of the refractory mold is a substance that has a high melting point (melting temperature). The melting point of the base material of the refractory mold is advantageously above 600 ° C, preferably above 900 ° C, in particular preferably above 1,200 ° C, and in particular preferably above 1,500 ° C.
    [0021] The base material of the refractory mold advantageously accounts for more than 80% by weight, especially more than 90% by weight, in particular preferably more than 95% by weight of the molding material mixture.
    [0022] A suitable sand is described, for example, in WO 2008/101668 A1 (= US 2010/173767 A1). Also suitable for use are regenerated, which can be obtained by washing and then drying of used fragmented molds. As a rule, the regenerates can make up at least about 70% by weight of the base material of the refractory mold, preferably at least about 80% by weight and in particular preferably more than 90% by weight.
    [0023] The average diameter of the base material of the refractory mold is generally between 100 μm and 600 μm. preferably between 120 μm and 550 μm and in particular preferably between 150 μm and 500 μm. The particle size can be determined, for example, by sieving in accordance with DIN ISO 3310. Particularly preferred are particle shapes with [ratio of] maximum linear dimension to minimum linear dimension (perpendicular to each other and in each case for all spatial directions) from 1: 1 to 1: 5 or 1: 1 to 1: 3, that is, those that, for example, are not fibrous.
    [0024] The base material of the refractory mold is preferably in a fluid condition, especially in order to allow processing in conventional core blasting machines.
    [0025] Water glasses contain dissolved alkaline silicates and can be produced by dissolving vitreous lithium, sodium and potassium silicates in water. The water glass preferably has a SiO2 / M2O molar formula (cumulative, in the case of different M's, that is, in total) in the range of 1.6 to 4.0, especially 2.0 less than 3.5, in that M represents lithium, sodium and / or potassium. Binders can also be based on water glasses that contain more than one of the alkaline ions mentioned, for example, lithium-modified water glasses known from DE 2652421 A1 (= GB1532847 A). Furthermore, water glasses can also contain polyvalent ions, for example, aluminum modified water glasses described in EP 2305603 A1 (= WO 2011/042132 A1). According to a particular embodiment, a proportion of lithium ions, especially lithium silicates, lithium oxides and amorphous lithium hydroxide, or a [Li2O] / [M2O] or [Li2Oactive] / [M2O] as described in DE 102013106276 A1 is used.
    [0026] Water glasses have a solids fraction in the range of 25 to 65% by weight, preferably from 30 to 55% by weight, especially from 30 to 50% by weight and above all in particular preferably from 30 to 45 % by weight.
    [0027] The solids fraction is based on the amounts of SiO2 and M2A present in the water glass. Depending on the application and the desired fluid level, between 0.5% by weight and 5% by weight of the water glass-based binder is used, advantageously between 0.75% by weight and 4% by weight, in particular preferably between 1% by weight and 3.5% by weight and in particular preferably 1 to 3% by weight, based on the base material of the mold. These values are based on the total amount of the binder water glass, including the solvent or diluent (especially aqueous) and the (possible) fraction of solids (total = 100% by weight). For the purposes of calculating the total preferred amount of water glass, for the above values, a solids content of 35% by weight (see examples) should be considered, regardless of the solids content actually used.
    [0028] Powder or particulate are the terms applied respectively to a solid powder (including dust) and granular material, which is fluid and thus can also be sieved or classified.
    [0029] The mixture of solids according to the invention contains one or more oxide compounds of powdered boron. The average particle size of the oxide boron compounds is advantageously less than 1 mm, preferably less than 0.5 mm, and in particular preferably less than 0.25 mm. The particle size of oxide boron compounds is advantageously greater than 0.1 μm, preferably greater than 1 μm and in particular preferably greater than 5 μm.
    [0030] The average particle size can be determined by means of sieve analysis. Preferably, the classification residue on a sieve with a mesh size of 1.00 mm is less than 5% by weight, in particular preferably less than 2.0% by weight and in particular preferably less than 1.0% by weight . In particular, preferably the residue of the classification on a sieve with a mesh size of 0.5 mm, regardless of the statements presented, is advantageously less than 20% by weight, preferably less than 15% by weight, in particular preferably less than 10% by weight and in particular preferably less than 5% by weight. In particular, preferably the residue of the classification on a sieve with a mesh size of 0.25 mm, regardless of the statements presented, is less than 50% by weight, preferably less than 25% and in particular preferably less than 15% by weight. The determination of the classification residue is done using the machine sieving method described in DIN 66165 (part 2), in which additionally a chain ring is used as a sieving aid.
    [0031] Oxidic boron compounds are defined as compounds in which boron is present in the +3 oxidation state. In addition, boron is coordinated with oxygen atoms (in the first coordination sphere, that is, as closest neighbors) - both by 3 and 4 oxygen atoms.
    [0032] Preferably, the oxide boron compound is selected from the group of borates, boric acids, boric acid anhydrides, borosilicates, borophosphates, borophosphosilicates and mixtures thereof, wherein the oxide boron compound preferably does not contain any organic groups.
    [0033] Boric acids are defined as orthoboric acid (general formula H3BO3) and meta or polyboric acids (general formula (HBO2) n). Orthoboric acid occurs, for example, in hot springs and as the mineral sassolin. It can also be produced from borates (eg, borax) by acid hydrolysis. Meta- and poly-boric acids can be produced, for example, from ortho-boric acid by heat-induced intermolecular condensation.
    [0034] Boric acid anhydride (general formula B2O3) can be prepared by calcination of boric acids. In this case, boric anhydride is obtained as a normally glassy hygroscopic mass that can subsequently be ground.
    [0035] Borates are theoretically derived from boric acids. They can be of natural or synthetic origin. Borates are constituted, among other things, of structural units of borate, in which the boron atom is surrounded by both 3 and 4 oxygen atoms as closest neighbors. The individual structural units are normally anionic and can be present with a substance both isolated, for example, in the form of orthborate [BO3] 3-, or linked together, for example, metaborates [BO2] nn, whose units can be joined together to form rings or chains - if a linked structure like this with corresponding BOB bonds is considered, it is generally anionic.
    [0036] Preferably, borates containing linked B-O-B units are used. Orthborates are suitable, but not preferred. Counterions for anionic borate units can be, for example, alkaline or alkaline earth cations, but also, for example, zinc cations.
    [0037] In the case of monovalent or divalent cations, the molar ratio of cation to boron can be described as follows: where M represents the cation and x is 1 for divalent cations and 2 for monovalent cations. The MxO: B2O3 molar ratio of (x = 2 to M = alkali metals and x = 1 to M = alkaline earth metals): B2O3 can vary within wide limits, but it is advantageously less than 10: 1, preferably less than 2: 1 . The lower limit is advantageously greater than 1:20, preferably greater than 1:10, and in particular preferably greater than 1: 5.
    [0038] Also suitable are borates in which trivalent cations serve as counterions for anionic borate units, for example, aluminum cations in the case of aluminum borates.
    [0039] Natural borates are normally hydrated, that is, they contain water as structural water (like OH groups) and / or as crystallization water (H2O molecules). As an example, borax or borax decahydrate (disodium tetraborate decahydrate) can be mentioned, whose general formula is reported in the literature both as [Na (H2O) 4] 2 [B4O5 (OH) 4] and, for the sake of simplicity, like Na2B4O7 * 10H2O. Both hydrated and non-hydrated borates can be used, but hydrated borates are preferably used.
    [0040] Both amorphous and crystalline borates can be used. Amorphous borates are defined, for example, as alkaline or alkaline earth borates.
    [0041] Perborates are not preferred because of their oxidative properties. The use of fluorborates is also theoretically possible, but not preferred, due to its fluorine content, especially in aluminum smelting. Since significant amounts of ammonia are released when ammonium borate is used with a glass solution of alkaline water, creating a health hazard to foundry workers, a substance like this is not preferred.
    [0042] Borosilicates, borophosphates and borophosphosilicates comprise compounds that are basically amorphous / vitreous.
    [0043] The structures of these compounds not only include coordinated ions of neutral boron-oxygen and / or anionic (for example, neutral BO3 units or BO4-anionic units), but also coordinated silicon-oxygen and / or phosphorus-oxygen ions neutral and / or anionic - silicon is in the +4 oxidation state and phosphorus is in the +5 oxidation state. The coordinated ions can be connected to each other by linking oxygen atoms, for example, in Si-O-B or in P-O-B. Metal oxides, especially alkaline and alkaline earth metal oxides, can be incorporated into the borosilicate structure, serving as so-called network modifiers. Preferably, the boron fraction (calculated as B2O3) in borosilicates, borophosphates and borophosphosilicates is greater than 15% by weight, preferably greater than 30% by weight, in particular preferably more than 40% by weight, based on the total mass of borosilicate corresponding borophosphate or borophosphosilicate.
    [0044] However, from the group of borates, boric acids, boric anhydride, borosilicates, borophosphates and / or borophosphosilicates, alkaline and alkaline earth borates are clearly preferred. One reason for this selection is the high hygroscopicity of boric anhydride, which prevents its possible use as powder additives in the case of prolonged storage. Furthermore, it has been observed in smelting experiments with an aluminum bath that borates lead to smelting surfaces distinctly better than boric acids and, therefore, the latter are less preferred. Borates are in particular preferably used. Especially preferably, alkaline and / or alkaline earth borates are used, among which sodium borates and / or calcium borates are preferred.
    [0045] Surprisingly, it was observed that even very small additions in the mixture of molding material can remarkably improve the disintegration of the casting mold after thermal stress, that is, after the casting of the metal, especially after the casting of aluminum. The fraction of the boric oxide compound in relation to the base material of the refractory mold is advantageously less than 1.0% by weight, preferably less than 0.4% by weight, in particular preferably less than 0.2% by weight, and in particularly preferably less than 0.1% and especially in particular preferably less than 0.075% by weight. The lower limit in each is advantageously greater than 0.002% by weight, preferably greater than 0.005% by weight, in particular preferably greater than 0.01% by weight and especially in particular preferably preferably greater than 0.02% by weight.
    [0046] It has also been surprisingly found that alkaline earth borates, especially calcium metaborate, increase the resistance of molds and / or cores cured with acidic gases such as CO2. It has also been unexpectedly observed that the moisture resistance of molds and / or cores is improved by the addition of oxide boron compounds according to the invention.
    [0047] The molding material mixture according to the invention contains a fraction of particulate amorphous silicon dioxide to increase the resistance level of the foundry molds produced with mixtures of this type of molding material. Increased resistances of foundry molds, especially increased hot resistances, can be advantageous in the automated manufacturing process. Synthetically produced amorphous silicon dioxide is particularly preferred.
    [0048] The particle size of amorphous silicon dioxide is advantageously less than 300 μm, preferably less than 200 μm, in particular preferably less than 100 μm and has, for example, an average primary particle size between 0.05 μm and 10μm. The residue from the classification of particulate amorphous SiO2 when passed through a sieve with a mesh size of 125 μm (120 mesh) is advantageously not more than 10% by weight, in particular preferably not more than 5% by weight and well in particularly preferably not more than 2% by weight. Regardless of this, the classification residue on a sieve with a mesh size of 63 μm is less than 10% by weight, advantageously less than 8% by weight. The determination of the classification residue is preferably made according to the machine screening method described in DIN 66165 (part 2), in which a chain ring is additionally used as a screening aid.
    [0049] Particulate amorphous silicon dioxide advantageously used in accordance with the present invention has a water content of less than 15% by weight, especially less than 5% by weight and in particular preferably less than 1% by weight.
    [0050] Amorphous particulate SiO2 is used as a powder (including dust).
    [0051] Both synthetically produced and naturally occurring silicas can be used as amorphous SiO2. The latter are known, for example, from DE 102007045649, but are not preferred, as they usually contain considerable crystalline fractions and are therefore classified as carcinogenic. Synthetic is the term applied to amorphous SiO2 that does not occur naturally, that is, whose production comprises a chemical reaction deliberately carried out by a human being, for example, the production of silica sols by ion exchange processes from solutions alkaline silicate, precipitation of alkaline silicate solutions, silicon tetrachloride flame hydrolysis, reduction of quartz sand with coke in an electric arc furnace in the manufacture of ferrosilicon and silicon. Amorphous SiO2 produced according to the two methods mentioned last is also known as pyrogenic SiO2.
    [0052] Occasionally, the term "synthetic amorphous silicon dioxide" is interpreted to include only precipitated silica (CAS No. 112926-00-8) and SiO2 produced by flame hydrolysis (Pyrogenic Silica, Smoked Silica, CAS No. 112945-52-5), while the product produced in ferrosilicon and silicon is only called amorphous silicon dioxide (Smoked Silica, Microsilica, CAS No. 69012-64-12). For the purposes of the present invention, the product produced during the manufacture of ferrosilicon and silicon is also called amorphous SiO2.
    [0053] Preferably used are precipitated silicas and Pyrogenic Silica, that is, silicon dioxide produced by hydrolysis by flame or in an electric arc. In particular preferably, amorphous silicon dioxide produced by thermal decomposition of ZrSiO4 (described in DE 102012020509) and SiO2 produced by oxidation of metallic Si with an oxygen-containing gas (described in DE 102012020510) are used. Also preferred is powdered quartz glass (primarily amorphous silicon dioxide), made from crystalline quartz by melting and rapidly cooling again, so that the particles present are spherical, rather than live (described in DE 102012020511). The average primary particle size of particulate amorphous silicon dioxide can be between 0.05 μm and 10 μm, especially between 0.1 μm and 2 μm. The primary particle size can be determined, for example, using dynamic light scattering (for example, Horiba LA 950) and verified by scanning electronic photomicrographs (SEM photographs using, for example, FEI company Nova NanoSEM 230). Furthermore, using SEM photographs, details of the primary particle size up to the order of magnitude of 0.01 μm can become visible. For SEM measurements the silicon samples were dispersed in distilled water and then applied to an aluminum support laminated with copper tape before the water was evaporated.
    [0054] In addition, the specific surface of particulate amorphous silicon dioxide was determined by gas adsorption measurements (BET method) according to DIN 66131. The specific surface of particulate amorphous SiO2 is between 1 and 200 m2 / g, especially between 1 and 50 m2 / g, in particular preferably between 1 and 30 m2 / g. If desired, the products can also be mixed, for example, to systematically obtain mixtures with certain particle size distributions.
    [0055] Depending on the manufacturing method and the producer, the purity of amorphous SiO2 can vary widely. Suitable types were considered to be those containing at least 85% by weight of silicon dioxide, preferably at least 90% by weight and in particular preferably at least 95% by weight. Depending on the use and the desired level of solids, between 0.1% by weight and 2% by weight of the particulate amorphous SiO2 is used, advantageously between 0.1% by weight and 1.8% by weight, in particular preferably between 0.1 % by weight and 1.5% by weight, in each case based on the base material of the mold.
    [0056] The ratio of water glass binder to particulate amorphous silicon dioxide can be varied within wide limits. This offers the advantage that the initial core strengths, that is, the strength immediately after removal of the molding tools, can be greatly improved without substantially affecting the final strengths. This is of great interest, especially in the case of light metal casting. On the one hand, high initial resistances are desired to transport the males without difficulty after they are produced or to combine them in complete male packages, while on the other hand, the final resistances should not be too high in order to avoid problems with breaking of the core after replicate casting, that is, after casting it must be possible to remove the base material from the mold without problems from the cavities of the casting mold.
    [0057] Based on the total amount of water glass of the binder (including diluent and solvent), amorphous SiO2 is advantageously present in a fraction of 1 to 80% by weight, advantageously 2 to 60% by weight, in particular preferably of 3 to 55% by weight and in particular preferably between 4 and 50% by weight. Or, regardless of this, based on the ratio of the fraction of water glass solids (based on oxides, ie total weight of alkali metal oxide and silicon dioxide) to amorphous SiO2 from 10: 1 to 1: 1.2 ( parts by weight).
    [0058] According to EP 1802409 B1, the addition of amorphous silicon dioxide can occur directly in the refractory both before and after the addition of binder, but moreover, as described in EP 1884300 A1 (= US 2008/029240 A1 ), a pre-mixture of SiO2 with at least part of the binder or sodium hydroxide is first produced, and this is then added to the refractory material. The binder or fraction of binder that may still be present and that has not been used for the premix can be added to the refractory material before or after adding the premix or together with it. The amorphous SiO2 should advantageously be added to the refractory solid before adding the binder.
    [0059] In an additional embodiment, barium sulfate can be added to the molding material mixture to further improve the surface of the casting, especially made of aluminum.
    [0060] Barium sulphate can be synthetically produced or natural barium sulphate, that is, it can be added in the form of minerals containing barium sulphate, such as heavy spar or barite. This and other features of the suitable barium sulfate as well as the molding material mixture made with it are described in more detail in DE 102012104934, and the content of their description is therefore also incorporated by the reference in the description of the present patent application. Barium sulfate is preferably added in an amount of 0.02 to 5.0% by weight, in particular preferably 0.05 to 3.0% by weight, in particular preferably 0.1 to 2.0% by weight or 0.3 to 0.99% by weight, in each case based on total mixtures of impression material.
    [0061] In an additional embodiment, at least aluminum oxides and / or mixed aluminum / silicon oxides in particulate form or aluminum and zirconium metal oxides in particulate form can be added to the molding material according to concentrations between 0.05% by weight and 4.0% by weight, advantageously between 0.1% by weight and 2.0% by weight, in particular preferably between 0.1% by weight and 1.5% by weight. weight, and in particular preferably between 0.2% by weight and 1.2% by weight, in each case based on the base material of the mold, especially by means of the additive component (A), as described in further detail in DE 102012113073 or DE 102012113074.
    [0062] Thus, these documents are also included by the reference as descriptions for the present patent. By means of such additives, after metal casting, molded parts, especially made of iron or steel with very high surface quality can be obtained, so that, after removing the casting mold, little or no post-processing of the surface of the casting is required.
    [0063] In an additional embodiment, a mixture of molding material according to the invention may comprise a phosphorus-containing compound. This additive is preferred in the case of very thin wall sections of a casting mold. Such additives are preferably inorganic phosphorus compounds, where phosphorus is preferably present in the +5 oxidation state.
    The phosphorus-containing compound preferably exists in the form of a phosphate or phosphorus oxide. The phosphate can be present as an alkali metal or alkaline earth phosphate, where alkali metal phosphates and especially the sodium salts thereof are particularly preferred.
    [0065] Orthophosphates as well as polyphosphates, pyrophosphates or metaphosphates can be used as phosphates. For example, phosphates can be produced by neutralizing the corresponding acids with an appropriate base, for example, an alkali metal base, such as NaOH, or possibly an alkaline earth metal base, where not necessarily all negative phosphate charges have to be saturated. Both metal phosphates and metal hydrogen phosphates, as well as metal dihydrogen phosphates can be used, for example, Na3PO4, Na2HPO4 and NaH2PO4. Anhydrous phosphates and phosphate hydrates can be used. Phosphates can be introduced into the molding material mixture in crystalline or amorphous form.
    [0066] Polyphosphates are considered especially linear phosphates having more than one phosphorus atom, in which phosphorus atoms are connected to each other by means of oxygen bonds.
    [0067] Polyphosphates are obtained by condensing orthophosphate ions with water division, so that a linear chain of PO4-tetrahedral is obtained, which are connected by their respective corners. Polyphosphates have the general formula (O (PO3) n) (n + 2) -, where n corresponds to the chain length. A polyphosphate can comprise up to several hundred PO4-tetrahedral. However, polyphosphates with shorter chain lengths are preferably used. Preferably, n has values of 2 to 100, in particular preferably 5 to 50. More highly condensed polyphosphates can also be used, that is, polyphosphates in which the tetrahedral PO4 are connected to each other by more than two corners and therefore exhibit polymerization in two. or three dimensions.
    [0068] Metaphosphates are defined as cyclic structures consisting of PO4-tetrahedral, each connected to each other by its corners. Metaphosphates have the general formula ((PO3) n) n-, where n is at least 3. Preferably n has values from 3 to 10, individual phosphates can be used, as well as mixtures of different phosphates and / or phosphorus oxides.
    [0069] The preferred fraction of the phosphorus-containing compound, based on the base material of the refractory mold, reaches between 0.05 and 1.0% by weight. Preferably, the fraction of phosphorus-containing compound is selected between 0.1 and 0.5% by weight. The phosphorus-containing organic compound preferably contains between 40 and 90% by weight, in particular preferably between 50 and 80% by weight phosphorus, calculated as P2O5. The phosphorus-containing compound itself can be added to the molding material mixture in solid or dissolved form. The phosphorus-containing compound is preferably added to the molding material mixture as a solid.
    [0070] According to an advantageous embodiment, the molding material mixture according to the invention contains a fraction of scaly lubricants, especially graphite or M0S2. The amount of scaly lubricant added, especially graphite, advantageously amounts to 0.05 to 1% by weight, in particular preferably 0.05 to 0.5% by weight, based on the base material of the mold.
    [0071] According to an additional advantageous modality, active surface substances, especially surfactants, which improve the flow properties of the molding material mixture can also be used. Suitable representatives of these compounds are described, for example, in WO 2009/056320 (= US 2010/0326620 A1). Preferably, anionic surfactants are used for mixing molding material according to the invention. Here, especially surfactants with sulfuric acid or sulfonic acid groups can be mentioned. In the mixture of solids according to the invention, the pure active surface material, especially the surfactant, based on the weight of the base material of the refractory mold, is preferably present in a fraction of 0.001 to 1% by weight, in particular preferably 0 , 01 to 0.2% by weight.
    [0072] The molding material mixture according to the invention represents an intensive mixing of at least the mentioned components. The particles of the base material of the refractory mold are advantageously coated with a layer of the binder. By evaporating the water present in the binder (approximately 40 to 70% by weight), based on the weight of the binder), firm cohesion between the particles of the base material of the refractory mold can be achieved.
    [0073] Despite the high strengths obtained with the binder system according to the invention, the foundry molds produced with the mixture of solids according to the invention after casting have surprisingly very good disintegration, especially in aluminum casting. As already explained, it was also observed that foundry molds can be produced with the molding material mixture according to the invention that show very good disintegration, even in ferrous foundry, so that the molding material mixture afterwards of the casting can be immediately poured again even from narrow and angular portions of the casting mold. The use of molded articles produced from the mixture of molding material according to the invention is therefore not merely limited to light metal casting or non-ferrous metal casting. Foundry molds are generally suitable for the casting of metals, for example, non-ferrous metals or ferrous metals. However, the mixture of solids according to the invention is in particular preferably suitable for aluminum casting.
    [0074] The invention also relates to a method for producing foundry molds for metal processing, in which the mixture of molding material according to the invention is used. The method according to the invention comprises the steps of: - preparing the aforementioned molding material mixture by combining and mixing at least the aforementioned mandatory components; - forming the molding material mixture; - cure the formed molding material mixture, in which the cured casting mold is obtained.
    [0075] In the production of the mixture of molding material according to the invention, in general, the procedure is followed in which first the base material of the refractory mold (component (F)) is supplied and then, under agitation, the binder or component (B) and the additive or component (A) are added. They can be dosed individually or as a mixture. According to a preferred embodiment, the binder is prepared as a two-component system, in which a first fluid component contains the water glass and optionally a surfactant (see the preceding one) (component (B)) and a second solid component contains one or more oxide boron compounds and the particular silicon dioxide (component (A)) and all other solid additives mentioned above in addition to the mold base material, especially particulate amorphous silicon dioxide and optionally a phosphate and optionally a preferably scaly lubricant and optionally barium sulfate or optionally other components as described.
    [0076] In the production of the molding material mixture, the base material of the refractory mold is placed in a mixer and then preferably the solid component (s) of the binder is (are) added and mixed (s) with the base material of the refractory mold. The mixing duration is selected in such a way that an intimate mixture of the base material of the refractory mold and a solid binder component occurs. The mixing duration depends on the amount of mixing molding material to be produced as well as the mixing unit used. The mixing time is preferably selected between 1 and 5 minutes.
    [0077] Then, preferably still further moving the mixture, the fluid component of the binder is added, and then the mixture is further mixed until a uniform layer of the binder has been formed in the granules of the base material of the refractory mold.
    [0078] Here also the mixing duration depends on the quantity of the molding material mixture to be used and the mixing unit used. Preferably, the duration of the mixing process is selected between 1 and 5 minutes. A fluid component is defined as both a mixture of several fluid components and the totality of all individual fluid components, where the latter can also be added individually. Similarly, a solid component is defined as both the mixture of individual components and all of the above-described solid components and the totality of all individual solid components, where the latter can be added to the molding material mixture both simultaneously and sequentially. According to another embodiment, first the fluid components of the binder can be added to the base material of the refractory mold, and only then the solid component of the mixture is added. According to another embodiment, first 0.05 to 0.3% by weight of water, based on the weight of the base material of the mold, is added to the base material of the refractory mold, and only then the solid and liquid components of the binder .
    [0079] In this modality, a surprisingly positive effect on the processing time of the mixture of solids can be achieved. The inventors consider that the effect of removing water from the solid components of the binder is reduced in this way and the curing process is thus delayed. The molding material mixture is then placed in the desired mold. In this process, the usual molding methods are used. For example, the mixture of molding material can be blasted on the molding tool with compressed air using a tapping machine. The molding material mixture is then cured, in which all methods can be used that are known for water glass binder, for example, hot curing, CO2 or air gasification, or a combination of the two as well as a cure with liquid or solid catalysts. Hot curing is preferred.
    [0080] In hot curing, water is removed from the molding material mixture. In this way, it is considered that condensation reactions between silanol groups are also initiated, so that crosslinking of the water glass occurs.
    [0081] Heating can take place, for example, in a molding tool which advantageously has a temperature of 100 to 300 ° C, in particular preferably 120 to 250 ° C. It is already possible to fully cure the casting mold in the molding tool. However, it is also possible to cure the casting mold only in its marginal area, so that it has adequate strength to be able to be removed from the molding tool. The casting mold can then be fully cured by removing more water from it. This can occur, for example, in an oven. Water removal can also occur, for example, by evaporating water under reduced pressure.
    [0082] The curing of the casting molds can be accelerated by blowing hot air into the molding tool. In this modality of the method, rapid transport out of the water contained in the binder can be performed, so that the casting mold solidifies in periods of time suitable for industrial use. The temperature of the blown air advantageously reaches 100oC to 180oC, in particular preferably 120o to 150oC. The flow rate of the heated air is preferably adjusted in such a way that the casting mold is cured in periods suitable for industrial use. The time periods depend on the size of the foundry molds produced. Curing in less than 5 minutes, advantageously less than 2 minutes, is preferred. However, longer periods of time may be required for very large casting molds.
    [0083] Removing water from the molding material mixture can also be carried out or supported by heating the molding material mixture with microwave radiation. For example, it would be conceivable to mix the base material of the mold with the solid powder component (s), apply this mixture to a layered surface, and print the individual layers using a liquid binder component, especially glass of water, in which the layer-by-layer application of the solid mixture is in each case followed by a printing process using the liquid binder.
    [0084] At the end of this process, that is, after the end of the last printing operation, the total mixture can be heated in a microwave oven.
    [0085] The methods according to the invention are suitable in themselves for producing all the casting molds normally used in metal casting, thus, for example, cores and molds. It is also particularly advantageous to use this method to produce casting molds that have very thin wall sections.
    [0086] Foundry molds produced from the mixture of molding material according to the invention or the method according to the invention have high strength immediately after production, without the strength of the casting molds after curing is as high that there are problems in removing the casting mold after the casting has been made. Furthermore, these casting molds have high stability under high atmospheric humidity, that is, surprisingly, the casting molds can also be stored without problems for long periods. As an advantage, the casting mold has very high stability under mechanical stress, so that thin-walled sections of the casting mold can be implemented without becoming deformed by the metallostatic pressure during the casting process. An additional object of the invention is therefore a casting mold obtained by the above-described method of the invention.
    [0087] In the following, the invention will be described in more detail based on examples, without being limited to those. The fact that exclusively hot curing is described as the curing method is not a limitation. Examples 1) Effect of various powdered boron oxide compounds on bending strengths
    [0088] The so-called Georg Fischer test bars were produced to test a mixture of impression material. Georg Fischer's test bars are parallelepiped test bars with dimensions of 150 mm x 22.36 mm x 22.36 mm. The compositions of the molding material mixtures are given in Table 1. The following procedure was used to produce the Georg Fischer test bars: • The components listed in Table 1 were mixed in a laboratory paddle mixer (from Vogel & Schemmann AG, Hagen, DE). For this purpose, first the quartz sand was placed in a container and the water glass was added with agitation. The water glass used was a sodium water glass containing some potassium. Therefore, in the following tables, the modular formula is given as SiO2: M2O, where M gives the sum of sodium and potassium. After the mixture was stirred for one minute, amorphous SiO2 and optionally oxide powdered boron compounds were added with further stirring. Then, the mixture was stirred for another minute; • Molding material mixtures were transferred to the storage tank of a H 2.5 Hot Box blasting machine from Roperwerk-Gieβereimaschinen GmbH, Viersen, DE, whose molding tool was heated to 180oC; • Molding material mixtures were introduced into the molding tool using compressed air (500 kPa (5 bar)) and remained in the molding tool for another 35 seconds; • To speed up the curing of mixtures, during the last 20 seconds, hot air (200 kPa (2 bar)), 100oC at the tool inlet) was passed through the molding tool; • The impression tool has been opened and the test bars removed.
    [0089] To determine the bending strengths, the test bars were placed on a Georg Fischer resistance testing machine equipped with a 3-point bending device (DISA Industrie AG, Schaffhausen, CH) and the force that caused the break the test bar has been determined. Folding resistances were measured according to the following program: • 10 seconds after removal (hot resistance) • 1 hour after removal (cold resistance)
    [0090] After 24 hours storage of the males in the chamber acclimatized to 30oC and 60% relative humidity, in which the males were only placed in the acclimatized chamber after cooling (1 hour after removal). Table 1

    [0091] The meanings of the envelopes in Table 1 are as follows: a) Alkaline water glass with a modular formula SiO2: M2O molar of approximately 2.2; based on the total glass of water. Solid content of about 35% b) Microsilica POS BW 90 LD (amorphous SiO2, Possehl Erzkontor; formed during thermal decomposition of ZrSiO4) c) Boric acid, thermal grade (99.9% H3BO3, Cofermin Chemicals GmbH & Co. KG ) d) Etibor 48 (borax pentahydrate, Na2B4O7 * 5 H2O, Eti Maden Isletmeleri) e) Sodium metaborate 8 mol (Na2O-B2O3 * 8H2O, Borax Europe Limited) f) Borax decahydrate SP (Na2B4O7 * 10H2O7 - powder, Borax Europe Limited) g) Borax decahydrate (Na2B4O7 * 10H2O - granular, Borax Europe Limited, Eti Maden Isletmeleri) h) Lithium borate (99.998% Li2B4O7, Alfa Aesar) i) Calcium metabolite (Sigma Aldrich ) k) Alkaline water glass with a modular molar formula SiO2: M2O of approximately 2.2; based on the total water glass. Solid content of about 35%. - 0.5 PBW borax decahydrate g) are dissolved in this water glass before use in a way that forms a clear solution.
    [0092] The measured folding resistances are summarized in Table 2.
    [0093] Examples 1.01 and 1.02 illustrate the fact that a distinctly improved resistance level can be achieved by adding amorphous SiO2 (according to EP 1802409 B1 and DE 10201202509 A1). Comparison of examples 1.02 to 1.14 shows that the level of resistance is not noticeably affected by the addition of powdered boron oxide compounds.
    [0094] Examples 1.06 and 1.11 to 1.14 make it possible to demonstrate a slight worsening of the resistance level with an increase in the additive fraction according to the invention. However, the effect is very mild.
    [0095] Comparison of examples 1.01, 1.15 and 1.16 shows that the addition of boron compounds according to the invention alone, that is, without the addition of amorphous silicon dioxide, has a negative effect on resistances, especially hot and cold resistances. Hot resistances are also very low for automated mass production.
    [0096] Comparison of examples 1.02, 1.06 and 1.09 shows that the addition of boron compounds according to the invention has a precarious effect on hot and cold resistances if the molding material mixture contains amorphous silicon dioxide as an additive in dust. Surprisingly, however, the addition of the boron compound according to the invention in the molding material mixture improves the stability of the males produced with it. Table 2
    j) Improvement of disintegration behavior
    [0097] The effects of different powdered boron oxide compounds on the removal behavior of the male were investigated. The following procedure was used: • Georg Fischer test bars made from molding mixtures 1.01 to 1.14 in Table 1 were examined for their resistance to bending (in analogy to example 1 - no differences were found in relation to the values summarized in Table 2). • Then Georg Fischer's test bars, broken into two pieces approximately in half, each perpendicular to its length, were subjected to thermal stress in a muffle furnace (Naber Industrieofenbau) at a temperature of 650ºC for 45 minutes. • After removing the bars from the muffle furnace and following a subsequent cooling process to room temperature, the bars were placed in a so-called stirring sieve (sieve placed on an AS 200 digit vibrating sieve shaker, Retsch GmbH) with a mesh width of 1.25 mm. • Then the bars were shaken at a fixed amplitude (70% of the maximum possible setting (100 units)) for 60 seconds. • Both the residue in the sieve and the amount of material crushed in the collection tray (fraction without the core) were determined using a scale. The fraction without the nucleus as a percentage is given in Table 3.
    [0098] The respective values, each of which represents an average value of repeated determinations, are summarized in Table 3.
    [0099] Comparison of examples 1.01 and 1.02 shows that the disintegration behavior of the molds produced in this way is distinctly worsened by the addition of a particulate amorphous silicon dioxide in the molding material mixture. On the other hand, comparison of examples 1.02 to 1.09 clearly shows that the use of powdered boron oxide compounds leads to distinctly improved disintegration properties of water glass bonded molds. Comparison of examples 1.07 and 1.10 shows that it makes a difference whether the borate (in this case) was dissolved in the binder before it was used in the molding material mixture, or if the borate was added to the molding material mixture as a solid powder . An effect like this is surprising.
    [00100] Examples 1.06 and 1.11 to 1.14 clearly show that the disintegration behavior can be noticeably improved by increasing the fraction of the additive according to the invention. It is also clear that even small amounts of additive are sufficient to increase the disintegration capacity of the cured molding material mixture after thermal loading. Table 3
    权利要求:
    Claims (29)
    [0001]
    1. Multicomponent system to produce molds or cores, characterized by the fact that it comprises at least the following components (A), (B) and (F), being present spatially separated from each other: (A) a powder additive component (A) comprising at least - one or more oxide compounds of powdered boron and - particulate amorphous silicon dioxide and - no glass of water containing dissolved alkaline silicates, (B) a liquid binder component (B) comprising at least - glass of water containing water and dissolved alkaline silicates, and (F) a fluid refractory component (F) comprising - a base material of the refractory mold and - no water glass containing dissolved alkaline silicates, to obtain a mixture of molding material by grouping.
    [0002]
    2. Multicomponent system according to claim 1, characterized by the fact that the oxide boron compound is selected from the group consisting of borates, borophosphates, borophosphosilicates and mixtures thereof, and especially is a borate, preferably an alkaline borate and / or alkaline earth such as sodium borate and / or calcium borate, wherein the oxide boron compound most preferably does not contain organic groups.
    [0003]
    Multicomponent system according to one or more of claims 1 to 2, characterized by the fact that the oxide boron compound is made up of structural elements B-O-B.
    [0004]
    4. Multicomponent system according to one or more of claims 1 to 3, characterized by the fact that the oxide boron compound has an average particle size greater than 0.1 μm and less than 1 mm, advantageously greater than 1 μm and less than 0.5 mm, and in particular preferably greater than 5 μm and less than 0.25 mm.
    [0005]
    Multicomponent system according to one or more of claims 1 to 4, characterized in that the oxide boron compound, based on the base material of the refractory mold, is added or contained in an amount of more than 0.002% in weight and less than 1.0% by weight, preferably more than 0.005% by weight and less than 0.4% by weight, in particular preferably more than 0.01% by weight and less than 0.1% by weight and in particularly preferably more than 0.02% by weight and less than 0.075% by weight.
    [0006]
    6. Multicomponent system according to one or more of claims 1 to 5, characterized by the fact that the base material of the refractory mold comprises quartz, zirconia or chromite sand; olivine, vermiculite, bauxite, refractory clay, glass microglobules, granular glass, aluminum silicate microspheres and mixtures thereof and preferably consists of more than 50% quartz sand based on the base material of the refractory mold.
    [0007]
    Multicomponent system according to one or more of claims 1 to 6, characterized in that more than 80% by weight, preferably more than 90% by weight, and in particular preferably more than 95% by weight of the Multicomponents are the base material of the refractory mold.
    [0008]
    Multicomponent system according to one or more of claims 1 to 7, characterized by the fact that the base material of the refractory mold has an average particle diameter of 100 μm to 600 μm, preferably between 120 μm and 550 μm, determined by sieve analysis.
    [0009]
    9. Multicomponent system according to one or more of claims 1 to 8, characterized in that the particulate amorphous silicon dioxide has a surface area, determined according to BET, between 1 and 200 m2 / g, advantageously greater or equal to 1 m2 / g and less than or equal to 30 m2 / g, in particular preferably less than or equal to 15 m2 / g.
    [0010]
    10. Multicomponent system according to one or more of claims 1 to 9, characterized in that the particulate amorphous silicon dioxide, based on the total weight of the binder, is used in an amount of 1 to 80% by weight, advantageously between 2 and 60% by weight.
    [0011]
    Multicomponent system according to one or more of claims 1 to 10, characterized in that the particulate amorphous silicon dioxide has an average primary particle diameter determined by dynamic light scattering between 0.05 μm and 10 μm, especially between 0.1 μm and 5 μm, and in particular preferably between 0.1 μm and 2 μm.
    [0012]
    12. Multicomponent system according to one or more of claims 1 to 11, characterized by the fact that particulate amorphous silicon dioxide belongs to the group consisting of: precipitated silica, pyrogenic silica produced by flame hydrolysis or in an electric arc , silica produced by thermal degradation of ZrSiO4, silicon dioxide produced by oxidation of metallic silicon with an oxygen-containing gas, quartz glass powder with spherical particles produced from crystalline quartz by melting and rapid cooling again, and mixtures thereof.
    [0013]
    13. Multicomponent system according to one or more of claims 1 to 12, characterized in that the multicomponent system, in addition to particulate amorphous SiO2, contains other particulate metal oxides, preferably aluminum oxides, specially selected from one or more more of the elements in groups a) to d): a) corundum plus zirconium dioxide, b) zirconium mullite, c) zirconium corundum and d) aluminum silicate plus zirconium dioxide, preferably as part of component (A).
    [0014]
    14. Multicomponent system according to one or more of claims 1 to 13, characterized in that the multicomponent system contains particulate amorphous silicon dioxide • in quantities of 0.1 to 2% by weight, advantageously 0.1 to 1.5% by weight, in each case based on the base material of the mold, and regardless of them • 2 to 60% by weight, in particular preferably 4 to 50% by weight, based on the weight of the binder (including water) or component (B), in which the solids fraction of the binder reaches 20 to 55% by weight, advantageously 25 to 50% by weight.
    [0015]
    Multicomponent system according to one or more of claims 1 to 14, characterized in that the particulate amorphous silicon dioxide used has a water content of less than 5% by weight and in particular preferably less than 1% by weight. Weight.
    [0016]
    16. Multicomponent system according to one or more of claims 1 to 15, characterized in that in the water glass (including water) an amount of 0.75% by weight to 4% by weight, in particular preferably between 1% by weight and 3.5% by weight, soluble alkaline silicates are contained, in relation to the base material of the mold in the molding material mixture and in which more preferably independently, but advantageously in combination with the quoted values, the fraction of water glass in solids content is 0.2625 to 1.4% by weight, preferably 0.35 to 1.225% by weight, relative to the base material of the mold in the molding material mixture.
    [0017]
    17. Multicomponent system according to one or more of claims 1 to 16, characterized by the fact that the water glass has a modular molar formula SiO2 / M2O in the range of 1.6 to 4.0, especially 2.0 to less than 3.5, with M = lithium, sodium and / or potassium.
    [0018]
    18. Multicomponent system according to one or more of claims 1 to 17, characterized in that the multicomponent system also contains one or more compounds containing phosphorus, preferably from 0.05 to 1.0% by weight, in particular preferably 0.1 to 0.5% by weight, based on the weight of the base material of the refractory mold, preferably as part of component (A), and also independently of them, the phosphorus-containing compound is preferably added as a solid and not in dissolved form.
    [0019]
    19. Multicomponent system according to one or more of claims 1 to 18, characterized in that a curing agent is added, in particular at least one ester compound or phosphate compound, preferably as a component constituent (A ) or as an additional component.
    [0020]
    20. Multicomponent system according to one or more of claims 1 to 19, characterized in that the amorphous particulate silicon dioxide is synthetically produced amorphous particulate silicon dioxide.
    [0021]
    21. Method for producing molds or cores, characterized by the fact that it comprises: - providing a mixture of molding material by combining - a refractory mold material; - water glass as a binder; - particulate amorphous silicon dioxide; and - one or more oxide boron powdered compounds, - mixing; • introducing the molding material mixture into a mold, and curing the molding material mixture by heat curing with heat and water removal, in which the oxide boron compound is added as a solid powder to the molding material mixture .
    [0022]
    22. Method according to claim 21, characterized in that the mixture of molding material is introduced into the mold by means of a blasting machine using compressed air and the mold is a molding tool and the molding tool it is subjected to a stream with one or more gases, particularly CO2, or gases containing CO2, advantageously CO2 heated to more than 60 ° C and / or air heated to more than 60 ° C.
    [0023]
    23. Method according to claim 21 or 22, characterized in that, to cure, the molding material mixture is exposed to a temperature of 100 to 300 ° C, preferably 120 to 250 ° C, preferably for less 5 min, in which most preferably the temperature is produced at least partially by blowing heated air in a molding tool.
    [0024]
    24. Method according to one or more of claims 21 to 23, characterized in that the molding material mixture has been prepared by combining the components (A), (B) and (F) of the multi-component system according to at least at least one of claims 1 to 12, 14 to 17 and 20 and optionally the additional substances or mixtures of substance according to one or more of claims 13, 18 and 19, wherein the additional substances or mixtures of substances according to at least one of claims 13, 18 and 19 are added separately or as parts of components (A), (B) and (F).
    [0025]
    25. Method according to one or more of claims 21 to 24, characterized in that the hot curing occurs by heating and removing water by exposing the mixture of molding material to a temperature of 100 to 300 ° C.
    [0026]
    26. Method according to one or more of claims 21 to 25, characterized in that the oxide boron compound consists of structural elements B-O-B.
    [0027]
    27. Method according to one or more of claims 21 to 25, characterized in that the amorphous particulate silicon dioxide is synthetically produced amorphous particulate silicon dioxide.
    [0028]
    28. Method for constituting layers of bodies, characterized by the fact that it comprises: - mixture of at least the powder additive component (A) and the fluid solids component (F) as defined in claims 1 to 20 together with, among others, possibly other optional components according to these claims to form a mixture, - layer-by-layer application of the mixture on a surface in the form of layers, and - printing the layers with the liquid binder component (B), in which the layer application per layer of the mixture is in each case followed by a printing process using the liquid binder component (B).
    [0029]
    29. Method according to claim 28, characterized in that the curing is preferably carried out by means of microwave impact.
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    同族专利:
    公开号 | 公开日
    WO2015058737A2|2015-04-30|
    DE102013111626A1|2015-04-23|
    MX2016005300A|2016-08-08|
    KR102159614B1|2020-09-28|
    HUE048328T2|2020-07-28|
    US20160361756A1|2016-12-15|
    RU2016118813A3|2018-05-25|
    KR20160088315A|2016-07-25|
    RU2703746C2|2019-10-22|
    EP3060362A2|2016-08-31|
    EP3060362B1|2020-01-01|
    WO2015058737A3|2015-06-18|
    CN105828973A|2016-08-03|
    MX359164B|2018-09-18|
    JP2016533900A|2016-11-04|
    SI3060362T1|2020-07-31|
    JP6594308B2|2019-10-23|
    PL3060362T3|2020-07-13|
    RU2016118813A|2017-11-28|
    US9901975B2|2018-02-27|
    CN105828973B|2019-10-18|
    ES2778075T3|2020-08-07|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    GB1146081A|1966-02-11|1969-03-19|Foseco Int|Foundry moulds and cores|
    AU2236370A|1969-11-17|1972-05-18|Minerals, Binders, Clays Limited|Improvements in the co2 process for bonding, moulding and core sands in foundries|
    JPS5227093B2|1975-03-28|1977-07-18|
    CH616450A5|1975-11-18|1980-03-31|Baerle & Cie Ag|Binder based on aqueous alkali metal silicate solutions|
    US4226277A|1978-06-29|1980-10-07|Ralph Matalon|Novel method of making foundry molds and adhesively bonded composites|
    EP0111398B1|1982-12-11|1987-01-21|Foseco International Limited|Alkali metal silicate binder compositions|
    AT389249B|1985-06-20|1989-11-10|Petoefi Mgtsz|Additive for regulating the strength remaining after casting of water-glass-bound casting moulds and/or cores|
    SE520565C2|2000-06-16|2003-07-29|Ivf Industriforskning Och Utve|Method and apparatus for making objects by FFF|
    JP4785333B2|2000-09-25|2011-10-05|フォクセルジェットテクノロジーゲーエムベーハー|Parts production method by deposition method|
    JP2002219551A|2001-01-22|2002-08-06|Okamoto:Kk|Dissipating core and casting method using the same|
    DE102004042535B4|2004-09-02|2019-05-29|Ask Chemicals Gmbh|Molding material mixture for the production of casting molds for metal processing, process and use|
    DE102006036381A1|2006-08-02|2008-02-07|Minelco Gmbh|Molded material, foundry-molding material mixture and method for producing a mold or a molded article|
    DE102006049379A1|2006-10-19|2008-04-24|Ashland-Südchemie-Kernfest GmbH|Phosphorus-containing molding material mixture for the production of casting molds for metal processing|
    DE102007008149A1|2007-02-19|2008-08-21|Ashland-Südchemie-Kernfest GmbH|Thermal regeneration of foundry sand|
    DE102007027577A1|2007-06-12|2008-12-18|Minelco Gmbh|Molding material mixture, molded article for foundry purposes and method for producing a molded article|
    DE102007045649B4|2007-09-25|2015-11-19|H2K Minerals Gmbh|A method of making a mold and / or a core using comminuted natural particulate amorphous silicic materials in the foundry area and binder composition|
    DE102007051850A1|2007-10-30|2009-05-07|Ashland-Südchemie-Kernfest GmbH|Molding compound with improved flowability|
    PL2305603T3|2009-10-05|2014-08-29|Cognis Ip Man Gmbh|Soluble glass solutions containing aluminium|
    JP5933169B2|2010-10-01|2016-06-08|リグナイト株式会社|Binder coated refractory, mold, mold manufacturing method|
    JP5972634B2|2012-03-29|2016-08-17|株式会社ロキテクノ|Pleated filter manufacturing method|
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    RU2764908C1|2021-07-30|2022-01-24|Акционерное общество "Научно-производственная корпорация "Уралвагонзавод" имени Ф.Э. Дзержинского"|Method for curing liquid-glass mixture in the manufacture of molds and rods|
    法律状态:
    2019-07-30| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-12-08| B09A| Decision: intention to grant|
    2021-01-12| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 21/10/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    DE201310111626|DE102013111626A1|2013-10-22|2013-10-22|Mixtures of molding materials containing an oxidic boron compound and methods for producing molds and cores|
    DE102013111626.4|2013-10-22|
    PCT/DE2014/000530|WO2015058737A2|2013-10-22|2014-10-21|Molding material mixtures containing an oxidic boron compound and method for the production of molds and cores|
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