mixing mold material to produce molds and casting cores, and method for producing molds or casting c

专利摘要:
1/1 summary â € œmixing of mold material to produce molds and casting cores, method for production of molds or casting cores, mold or core, use of a mixture of mold material, and, a multi-component system for the production of molds or cores' the invention relates to mixtures of mold material containing at least one aluminum oxide in the alpha phase and / or at least one mixed aluminum oxide / silicon, except for mixed aluminum / silicon oxides with a layered silicate structure, such as a particulate metal oxide, in combination with refractory mold base materials and a binder system based on liquid glass. mixtures of mold material are used for the production of molds and cores for the foundry industry.
公开号:BR112015014668B1
申请号:R112015014668
申请日:2013-12-20
公开日:2020-01-28
发明作者:Deters Heinz；Zupan Henning；Oberleiter Martin
申请人:Ask Chemicals Gmbh；
IPC主号:

专利说明:

“MIXING MOLD MATERIAL TO PRODUCE CASTING MOLDS AND MACHINES, AND, METHOD FOR CASTING MOLDS OR CASTING MACHINES”
FIELD OF THE INVENTION [0001] The invention relates to mixtures of mold material containing at least one aluminum oxide in the alpha phase and / or at least one mixed aluminum / silicon oxide, except for mixed aluminum / silicon oxides with a layered silicate structure, such as a particulate metal oxide, in combination with base materials of refractory molds and a binder system based on soluble glass. Particulate metal oxides show little or no tendency to react with alkaline soluble glass at room temperature. Mold material mixtures are used for the production of molds and cores for the foundry industry.
Prior Art [0002] Foundry molds essentially consist of sets of molds and cores, which represent the negative shapes of the cast to be produced. These cores and molds consist of a refractory material, for example, quartz sand, and a suitable binder, which provides adequate mechanical resistance to the casting mold after removal of the molding tool. Therefore, a base material of refractory mold enveloped with a suitable binder is used for the production of foundry molds. The base material of the refractory mold is preferably used in fluid form, so that it can be filled into a suitable hollow mold and compacted therein. The binder produces firm cohesion between the particles of the mold base material, so that the casting mold will achieve the required mechanical stability.
[0003] Foundry molds have to meet several requirements. During the actual casting process, they first have to submit
Petition 870190118928, of 11/18/2019, p. 9/16 / 41 adequate resistance and thermal stability to accommodate the liquid metal in the hollow mold consisting of one or more (partial) casting molds. After the start of the solidification process, the mechanical stability of the casting is guaranteed by a layer of solidified metal that forms along the walls of the casting mold. The casting mold material now has to decompose under the influence of the heat released by the metal, so that it loses its mechanical strength, and thus the cohesion between individual particles of the refractory material is canceled out. In the ideal case, the casting mold decomposes again into fine sand, which can be easily removed from the casting.
[0004] Recently, moreover, there is an increasing demand that as much as possible no air pollution in the form of CO2 or hydrocarbons is released during the production of the casting and cooling, in order to protect the environment and limit the nuisance of odor in the environment due to hydrocarbons (mainly aromatics). In order to meet these demands, in recent years, inorganic binder systems have been developed, or additionally developed, whose use makes it possible to avoid the emission of CO2 and hydrocarbons during the production of metal molds, or at least minimize it. However, the use of inorganic binder systems often entails other drawbacks, which will be described in detail in the following comments.
[0005] Inorganic binders, in comparison with organic binders, have the drawback that the foundry molds produced from them have relatively low strength. This is particularly noticeable immediately after removing the casting mold from the tool. Good strengths at this point, however, are particularly important for the production of complicated and / or thin-walled moldings and their safe handling. Resistance to atmospheric moisture is also distinctly less compared to organic binders.
Petition 870190071668, of 7/26/2019, p. 15/67 / 41 [0006] DE 102004042535 A1 (US 7770629 B2) describes that greater initial strengths and greater resistance to atmospheric moisture can be achieved by using a refractory mold base material, a soluble glass-based binder and a fraction of a particulate metal oxide selected from the group of silicon dioxide, aluminum oxide, titanium oxide and zinc oxide. An extra detail is the use of particulate amorphous silicon dioxide.
[0007] Inorganic binder systems have the added drawback compared to organic binder systems that foundry molds produced from them often lead to marked adhesions and penetrations of sand into the melt, which is associated with considerable cleaning efforts and thus greater costs for foundries.
[0008] Furthermore, the demoulding behavior, that is, the ability of the casting mold to disintegrate rapidly (by applying mechanical stress) in a fluid form after metal casting is often less satisfactory in the case of casting molds produced from purely inorganic materials (for example, those using soluble glass as a binder) than in the case of casting molds produced with an organic binder. This property cited lastly, the worst demoulding behavior, is especially disadvantageous when thin or delicate or complex wall casting molds, which are theoretically difficult to remove after the casting is completed, are used. For example, so-called water-jacketed males, which are necessary to produce certain areas in internal combustion engines, can be mentioned.
[0009] It is also known that organic components that undergo pyrolysis or reaction due to the influence of hot metal and thus, on the one hand, facilitate the disintegration of the casting mold after casting by the formation of pores and, on the other hand, can lead to casting surfaces
Petition 870190071668, of 7/26/2019, p. 16/67 / 41 can be added to the mold material mixture. However, the use of organic components in mixtures of mold material leads to the emission of CO2 and other pyrolysis products during casting.
[00010] US 3203057 describes mixtures of mold material consisting of a fine refractory material, a liquid binder, in which this is especially an alkaline silicate solution, and an active substance containing Al2O3, which improves the mold release behavior after metal casting. Active substances containing Al2O3 are defined as pure aluminum oxide, known mixed oxides such as aluminosilicates, clay minerals such as bentonite or montmorillonite, active substances containing naturally occurring Al2O3 such as bauxite and other minerals such as cement and kaolin. The active substances containing Al2O3 are described here only in a very general way, and there is no precise information as to which of these substances are particularly well suited for the mold release capacity, the processing time of the mold material mixture, or surface casting quality of the castings in question.
[00011] US 4233076 describes mixtures of mold material consisting of sand, an alkaline silicate binder, at least one curing agent selected from the group of alkylene carbonate, an organic monocarboxylic or dicarboxylic acid or a methyl ester thereof, nou dicarboxylic acid or the methyl ester of this, carbon dioxide or blast furnace slag, and a substance containing Al2O3 of this, whose average particle size distribution falls between 0.2 and 5 pm.
[00012] It is described that the aluminum oxide-containing solid preferably has a BET surface area between 3 and 40 m ² / g. Al ₂ O3-3 H2O is described as preferred.
[00013] JP 4920794 B1 describes mixtures of mold material
Petition 870190071668, of 7/26/2019, p. 17/67 / 41 consisting of foundry sand, an alkaline silicate binder and amorphous spheroids made of acidic spherical aluminum oxide. These amorphous spheroids are supposed to act like so-called "superplasticizers" and support healing, ultimately resulting in increased resistance.
Problems with Prior Technology and Problem Statement [00014] The inorganic binder systems known so far for casting purposes still leave room for improvement. In particular, it is desirable to develop an inorganic binder system that:
(a) does not allow or allow at least a distinctly reduced amount of CO2 emissions and organic pyrolysis products, gaseous hydrocarbons and / or aerosols, for example, aromatics, to form during metal casting, (b) reaches an appropriate level of resistance , which is necessary in automated manufacturing processes, especially suitable heat resistance and resistance after storage, (c) makes possible a very good surface quality of the casting (even without the use of refractory coatings, so that powders are not required) -processing or at least only light post-processing, (d) leads to good disintegration characteristics of the casting mold after metal casting, so that the casting in question can be removed from the casting mold easily and without residue, ( e) in the case of hot curing and / or CO2 curing, it allows the longest possible processing time for the mixture of mold material produced with it, and (f) with a mold base material, produces a fluid mold material mixture, so that casting molds with complex geometry become possible.
Petition 870190071668, of 7/26/2019, p. 18/67 / 41 [00015] Therefore, the invention was based on the task of supplying a mixture of mold material to produce foundry molds for metal processing that meets the above requirements (a) - (f).
[00016] In particular, the mixture of mold material according to the invention is characterized by the fact that it improves the casting surface of the castings in question without resorting to the addition of organic additives. This observation can be made especially in the smelting of iron and steel, but also in the smelting of light metals and non-ferrous metals.
Summary of the Invention [00017] The above requirements are satisfied with a mixture of mold material with the resources of the independent claims. Advantageous additional embodiments of the mold material mixture according to the invention form the subject matter of the dependent claims or are described below.
[00018] The mixture of mold material according to the invention to produce foundry molds for metal processing comprises at least:
a) a base material of refractory mold;
b) an inorganic binder; and
c) at least one particulate metal oxide, in which the particulate metal oxide
- comprises or consists of at least one aluminum oxide in the alpha phase; and / or
- at least one mixed aluminum / silicon oxide, other than mixed aluminum / silicon oxides with a layered silicate structure.
[00019] Surprisingly, it has been observed that the addition of particulate aluminum and zirconium oxides, particularly together with amorphous particulate silicon dioxide, in the mold material mixture, makes it possible to produce foundry molds based on inorganic binders that have high
Petition 870190071668, of 7/26/2019, p. 19/67 / 41 resistance both immediately after production and with prolonged storage. A particular advantage is based on the fact that, after metal casting, a cast part, particularly made of iron or steel, with very high surface quality, is obtained, so that, after removing the casting mold, it is little or no post-processing of the casting surface is required.
[00020] The surface quality of the cast in question made of iron or steel is sometimes flush with those surfaces that can be produced with the help of organically bonded casting molds coated with a refractory layer. A refractory lining can be achieved with so-called starches, which have to be applied to the casting molds after they are produced. The advantage of the mixture of mold material produced according to the invention thus is based on the fact that at least one coating process can be eliminated, which means substantial cost savings for the respective foundries.
[00021] The mold material mixture preferably does not contain any organic components, so that no emissions of CO2 and other pyrolysis products occur. For this reason, pollution, particularly in the workplace, from emissions that are harmful to health can be reduced.
[00022] The use of the mixture of mold material according to the invention also contributes to reduce harmful emissions to the climate (by CO2 and other organic products of pyrolysis).
[00023] Particulate metal oxide has no or at least very low reactivity with the inorganic binder, particularly alkaline soluble glass.
Detailed Description of the Invention [00024] The usual materials can be used as base material for
Petition 870190071668, of 7/26/2019, p. 20/67 / 41 refractory mold to produce foundry molds. The following, for example, are suitable: quartz sand or chromium ore, olivine, vermiculite, bauxite and refractory clay, particularly more than 50% by weight of quartz sand based on the base material of refractory mold. It is not necessary to exclusively use new sand. Of course, to save resources and avoid landfill costs, it is still advantageous to use the highest possible fraction of regenerated used sand. The refractory mold base material preferably constitutes more than 80% by weight, particularly more than 90% by weight of the mixture of mold material.
[00025] A suitable regenerated sand is described, for example, in WO 2008/101668 (= US 2010/173767 A1). Also suitable are regenerates obtained by washing and then drying. Usable, but less preferred, are regenerated obtained by purely mechanical treatment. As a rule, the regenerate can replace at least about 70% by weight of the new sand (in the base material of refractory mold), preferably at least about 80% by weight and in particular preferably at least about 90% by weight.
[00026] Regenerates of the refractory mold base material which have been heated to a temperature of at least 200 ° C for regeneration and particularly which have changed during this heat treatment are preferred. [00027] Furthermore, synthetic mold materials can also be used as base materials for refractory molds, for example, glass microspheres, glass granules, or spherical ceramic mold base materials or hollow aluminum silicate microspheres (as well called microspheres) known as "Cerabeads" or "Carboaccucast". Such hollow aluminum silicate microspheres are sold, for example, by Omega Minerals Germany GmbH, Norderstedt, in varying degrees with different levels of aluminum oxide under the name OmegaSpheres ”. Corresponding products are available, for example, through PQ
Petition 870190071668, of 7/26/2019, p. 21/67 / 41
Corporation (USA) under the name "ExtendoSpheres".
[00028] The average diameter of the base materials of refractory molds as a rule is between 100 μιιι and 600 gm, preferably between 120 gm and 550 μιιι and in particular preferably between 150 gm and 500 μιιι. The average particle size can be determined, for example, by sieve analysis according to DIN 66165 (Part 2) with analytical sieves according to DIN ISO 3310-1. Particularly preferred are particle shapes with ratios from the largest longitudinal dimension to the smallest longitudinal dimension (in arbitrary spatial directions) from 1: 1 to 1: 5 or 1: 1 to 1: 3, that is, those that are not, for example , fibrous.
[00029] In casting experiments, particularly with aluminum, it has been observed that synthetic base mold materials, especially glass microspheres, glass granules or microspheres, can contribute to creating smoother casting surfaces. In this case, it is not necessary to produce the entire mold base material from the synthetic mold base material. The preferred fraction of the synthetic mold base material is at least about 3% by weight, advantageously at least 5% by weight, in particular advantageously at least 10% by weight, preferably at least about 15% by weight, and in particular preferably at least about 20% by weight, based on the total amount of the refractory mold base material.
[00030] The base material of the refractory mold preferably has a fluid state, particularly to allow processing of the mixture of mold material according to the invention in conventional core blasting machines.
[00031] Glasses soluble as inorganic binders contain dissolved alkaline silicates and can be produced by dissolving lithium, sodium and / or glass-type potassium silicates in water. The soluble glass preferably has a molar fraction SiO2 / M2O in the range of 1.6 to 4.0, particularly 2.0 to less than 3.5, where M represents lithium, sodium or potassium. The binders
Petition 870190071668, of 7/26/2019, p. 22/67 / 41 can also be based on soluble glasses that contain more than one of the alkaline ions mentioned, such as lithium-modified soluble glasses known by DE 2652421 A1 (= GB1532847 A). In addition, soluble glasses can also contain multivalent ions, for example, Al modified soluble glasses described in EP 2305603 A1 (= WO 2011/042132 A1). Soluble glasses modified with B are also possible. Soluble glasses have a solids fraction in the range of 25 to 65% by weight, preferably from 30 to 60% by weight. The solids fraction is based on the amount of SiO2 and M2O contained in the soluble glass. Depending on the application and the desired strength level, between 0.5% by weight and 5% by weight of the soluble glass-based binder are used, preferably between 0.75% by weight and 4% by weight, in particular preferably between 1% by weight and 3.5% by weight, in each case based on the base mold material. The statements are based on the total amount of the soluble glass binder, including the solvent or diluent (particularly aqueous) and the fraction of solids, if any (= 100%).
[00032] It has been surprisingly observed that, because of the addition of the aforementioned particulate metal oxides in the mold material mixture, foundry molds based on inorganic binders can be produced which not only have high strength immediately after production and after storage prolonged, but also result in good surface quality of castings, especially those made of iron and steel.
[00033] Particulate metal oxides containing at least one aluminum oxide in the alpha phase; and / or at least one mixed aluminum / silicon oxide, other than mixed aluminum / silicon oxides with a layered silicate structure, are defined not only as particulate metal oxides consisting of pure aluminum oxide or pure aluminosilicates or aluminosilicates, but mixtures of the metal oxides mentioned
Petition 870190071668, of 7/26/2019, p. 23/67 / 41 with other oxides, for example those of zirconium, zirconium incorporated in mixed aluminum / silicon oxides, or mixtures of heterogeneous materials, that is, those consisting of several phases, which, among other things, consist of at least less than the following solids or phases: solids and phases containing aluminum oxide and / or containing aluminum oxide / silicon.
[00034] The particulate metal oxide according to the invention is preferably selected from the group of corundum plus zirconium dioxide, zirconium mullite, corundum - zirconium and aluminum silicates (other than those with layered silicate structure) plus zirconium and also optionally contains additional metal oxides.
[00035] The mixed aluminum / silicon oxide is also preferably a nesosilicate. Typical representatives of these nesosilicates are (according to Sistemaatik der Minerale nach Strunz [Strunz Mineralogical Tables], 9th ed.), For example, mullite (including fused mullite and sintered mullite, as well as Mullite containing ZrO2), silimanite and other elements of the group silimanite (for example, kyanite or andalusite), wherein in particular preferably kyanite from the silimanite group is used. Particularly preferred are an amorphous aluminum silicate (other than one with a layered silicate structure) with more than 50% atomic aluminum atoms based on the total of all silicon and aluminum atoms and a powder containing aluminum oxide, which is produced as a by-product of zirconium - corundum production and will be described in more detail below.
[00036] Aluminum silicates in the sense of this invention are defined as aluminosilicates and aluminosilicates.
[00037] In nesosilicates, the SiO4 (tetrahedral) fractions contained in the structure are not directly coupled together (without Si-O-Si bonds); instead, bonds of the tetrahedral SiO4 moieties on one or more Al atoms (Si-O-Al) are present. In the structure of the nesosilicates claimed here, the Al atoms are present in coordination 4, 5 and / or 6 times with
Petition 870190071668, of 7/26/2019, p. 24/67 / 41 oxygen atoms.
[00038] Mixed aluminum / silicon oxides with a layered structure, for example, metakaolin, kaolin and kaolinite are not suitable as additives for the binder. Also unsuitable is amorphous pyrogenic aluminum oxide.
[00039] The fineness of the particulate metal oxide according to the invention can be determined by sieving. Typically, the residue that does not pass through a 75 µm mesh size sieve (200 mesh) does not reach more than about 50% by weight, preferably no more than about 30% by weight, more preferably no more than about 20% by weight and in particular preferably not more than about 15% by weight.
[00040] The sieve residue is determined by sieve analysis according to DIN 66165 (Part 2) using a machine classification method, in which, according to one modality, sieving auxiliaries are not used, and according to with another embodiment, a chain ring is also used as a screening aid.
[00041] The particle shape of particulate metal oxides can basically be any shape, for example, fibrous, irregular, sharp corner, flocculate, rounded or rounded edge. Preferably, however, round or rounded edge particle shapes are preferred. Particularly preferably, round particle shapes are used, where they can be ellipsoidal or spherical - spherical are preferred here.
[00042] The ratio of the largest longitudinal dimension to the smallest longitudinal dimension of the respective particle shapes (for all directions in space) is preferably less than 10: 1, in particular preferably less than 5: 1 and in particular preferably less than 3 :1. Since spherical particle shapes are especially advantageous, a ratio of the largest longitudinal dimension to the smallest longitudinal dimension of 1.1: 1 to 1: 1 is ideal.
Petition 870190071668, of 7/26/2019, p. 25/67 / 41 [00043] The average primary particle size of the particulate metal oxides according to the invention which can be determined with SEM imaging and graphical evaluation is typically greater than 0.01 gm and preferably greater than 0.02 gm . This particle size is also typically less than 50 gm, preferably less than 20 gm, in particular preferably less than 10 gm and in particular preferably less than 5 gm.
[00044] Furthermore, the average specific surface area of the particulate metal oxides was determined using gas absorption measurements (BET method) according to DIN 66131. The specific surface of this substance is typically less than 50 m ² / g, preferably less than 30 m ² / g, in particular preferably less than 17 m ² / g. The specific surface of this substance is typically greater than 0.1 m ² / g, preferably greater than 0.5 m ² / g, and in particular preferably greater than 1 m ² / g.
[00045] Zirconium dioxide can be present in tetragonal or monoclinic modification.
[00046] In particular preferably, especially to produce smooth casting surfaces, a particulate metal oxide is used which forms as a by-product in the production of corundum - zirconium and will be described in more detail below. The main constituents of this dust are Al2O3, ZrO2 and SiO2, in which these oxides can be present in various modifications of the pure oxide or in the form of mixed oxides.
[00047] The aluminum fraction, calculated as AEO3, in particulate metal oxide or dust, is advantageously greater than 25% by weight, preferably greater than 30% by weight, in particular preferably preferably greater than 35% by weight and in particular preferably greater than 40% by weight. The fraction of aluminum, calculated as Al2O3, in particulate metal oxide or dust is usually less than 80% by weight, preferably less than 70% by weight, in particular preferably less than 65% by weight and
Petition 870190071668, of 7/26/2019, p. 26/67 / 41 in particular preferably less than 60% by weight.
[00048] The fraction of zirconium calculated as ZrO2 in particulate metal oxide or dust, to the extent it is present, is advantageously greater than 2% by weight, preferably greater than 4% by weight, in particular preferably greater than 8 % by weight. The fraction of zirconium calculated as ZrO ₂ in this dust is usually less than 50% by weight, preferably less than 40% by weight and in particular preferably less than 30% by weight.
[00049] The fraction of silicon (other than particulate amorphous silicon oxide), calculated as SiO2, in particulate metal oxide or dust, when present, is advantageously greater than 5% by weight, preferably greater than 15% by weight, and in particular preferably greater than 20% by weight. The fraction of silicon calculated as SiO2 in this dust is usually less than 60% by weight, preferably less than 50% by weight and in particular preferably less than 45% by weight.
[00050] Other oxides may also be present as contaminants in particulate metal oxide or dust, for example, Fe2O3, Na2O TiO2, MgO and CaO. The fraction of these contaminants according to one embodiment is usually less than 12% by weight, preferably less than 8% by weight and in particular preferably less than 4% by weight.
[00051] Aluminum is present in several phases in the heterogeneous dust of the production of corundum - zirconium. Corundum (a-AEOs) can be clearly determined as the crystalline phase by X-ray powder diffractometry. Such measurements can be made, for example, in a PANalytical inherent protection diffractometer (X'perl PW3040), equipped with a primary monochromator and a position sensitive detector. Small amounts of crystalline synthetic mullite (approximately Al ^ SU ^ O ^) can similarly be found using this method.
Petition 870190071668, of 7/26/2019, p. 27/67 / 41 [00052] In addition to these phases found by X-ray powder diffractometry, ²⁷ Al solid state NMR measurements indicate that additional aluminum-containing phases are present, which, according to the inventors' conjectures, are amorphous . Such measurements can be made, for example, using a BRUKER AVANCE DSX 500 spectrometer (magnetic flux density 11.74 Tesla) with the Magic-Angle-Spinning technique (MAS, about 25 kHz).
[00053] With scanning electron microscope images (SEM images produced, for example, with FEI's Nova NanoSEM 230), details of the primary particle shape can be viewed up to the order of magnitude of 0.01 gm. In addition to particles with living and irregular corners, a large number of spherical particles have been identified, which have a low degree of agglomeration and / or intergrowth with each other.
[00054] The average primary particle size of spherical particles of particulate metal oxides can be determined by SEM Images (by graphic analysis) and can reach between 0.01 pm and 10 gm, especially between 0.02 pm and 5 um, in particular preferably between 0.02 pm and 2 µm. By means of the EDX unit integrated in the scanning electron microscope, the elemental composition of the spherical particles can be determined by X-ray analysis of dispersive energy. The detection of secondary electrons was performed by a lens SE detector (TLD-SE). The X-ray analysis of dispersive energy was performed by an EDAX system. During this study, it was observed that most spherical particles consist of aluminum silicate.
[00055] The inventors suggest, without being bound by theory, that these spherical aluminum silicate particles are amorphous and that the presence of such particles in the mixture of mold material has an advantageous effect on their compaction and on the surface quality of the casting corresponding. This is observed both in cast iron and steel
Petition 870190071668, of 7/26/2019, p. 28/67 / 41 in an aluminum cast, and therefore the use of this dust containing aluminum oxide and zirconium oxide from the production of zirconium corundum is particularly preferred.
[00056] Aluminum oxide in the alpha phase and / or mixed aluminum / silicon oxide other than mixed aluminum / silicon oxide with layered silicate structure (optionally in total) according to the invention is always present between 0, 05% by weight and 2.0% by weight, preferably between 0.1% by weight and 2.0% by weight, in particular preferably between 0.1% by weight and 1.5% by weight and in particular preferably between 0.2% by weight and 1.2% by weight or even between 0.2% by weight and 0.8% by weight in the composition of the mold material, in each case based on the mold base material, is added in the composition of the mold material in the mentioned fractions. If aluminum oxide in the alpha phase and / or mixed aluminum / silicon oxide are used together, the limit values quoted apply to the sum of aluminum oxide in the alpha phase according to the invention and mixed aluminum / silicon oxide according to with the invention.
[00057] In an additional preferred embodiment, a fraction of a particulate amorphous SiO2 can be added to the mold material mixture according to the invention to increase the strength of the foundry molds produced with such mold material mixtures. An increase in the strength of the casting molds, particularly an increase in the resistance to hot, can be advantageous in the automatic manufacturing process. The particulate amorphous silicon dioxide advantageously has a particle size of 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 of between 0.05 µm and 10 qm.
[00058] The particle size can be determined by sieve analysis. In particular, preferably the residue of the classification in a sieve with a mesh size of 63 qm is less than 10% by weight,
Petition 870190071668, of 7/26/2019, p. 29/67 / 41 preferably less than 8% by weight.
[00059] The determination of the particle size of the classification waste is made by sieve analysis according to DIN 66165 (Part 2) using a mechanical classification method, in which, according to one modality, sieving aids are not used. and, according to another embodiment, a chain ring is also used as a screening aid. The primary particle size is determined by dynamic light scattering and can be verified by SEM.
[00060] Particulate amorphous silicon dioxide can be added together with particulate metal oxide, or separately. Regardless, it must be understood that the statements made here regarding the concentration of particulate metal oxide and particulate amorphous silicon dioxide are made without other component (s) respectively. In case of doubt, the component has to be calculated.
[00061] The amorphous SiO2 preferably 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. In particular, amorphous SiO ₂ is added as a powder.
[00062] The amorphous SiO ₂ used can be synthetically produced or naturally occurring silicas. However, the latter, known, for example, by DE 102007045649, are not preferred, as, as a rule, they contain substantial crystalline fractions and are therefore classified as carcinogenic.
[00063] Synthetic amorphous SiO2 is defined as non-naturally occurring material, that is, its production comprises a chemical reaction, for example, the production of silica sols by ion exchange processes from alkaline silicate solutions, precipitation at from alkaline silicate solutions, hydrolysis by silicon tetrachloride flame, reduction of quartz sand with coke in an electric arc furnace during the production of
Petition 870190071668, of 7/26/2019, p. 30/67 / 41 ferrosilicon and silicon. Amorphous S1O2 produced according to the two methods mentioned last is also known as pyrogenic SiO2. Sometimes synthetic amorphous SiO2 is defined only as precipitated silica (CAS-No. 112926-00-8) and SiO2 produced by flame hydrolysis (Pyrogenic Silica, Fumed Silica, CAS No. 112945-52-5), whereas the product produced during the manufacture of ferrosilicon or silicon is merely designated as amorphous SiO2 (Fumed Silica, Microsilica, CAS No. 69012-64-12). For the purpose of the present invention, the product obtained during the production of ferrosilicon or silicon will also be called amorphous SiO2.
[00064] Precipitated and pyrogenic SiO2, that is, the latter produced by hydrolysis by flame or in an electric arc furnace, are preferably used. Especially preferably used is amorphous SiO2 produced by thermal degradation of ZrSiO4 (cf. DE 102012020509: the zirconia fraction is added as ZiO2 to the particulate metal oxide, and the other fraction to the amorphous silicon dioxide) and SiO2 produced by oxidation of metallic Si using gases containing oxygen (cf. DE 102012020510). Also preferred is powdered quartz gas (mainly amorphous SiO2), produced from crystalline quartz by melting and rapid cooling, so that the particles are present in the spherical form, and not in the irregular form (cf. DE 102012020511). The average primary particle size of the synthetic amorphous silicon dioxide can be between 0.05 gm and 10 gm, particularly between 0.1 gm and 5 gm, in particular preferably between 0.1 gm and 2 gm. The primary particle size can be determined, for example, using dynamic light scattering (for example, Horiba LA 950) and verified by scanning electron microscope imaging (SEM images, for example, with FEI's Nova NanoSEM 230). In addition, details of the primary particle shape can be viewed up to the order of magnitude of 0.01 gm using SEM imaging. For SEM measurements, SiO2 samples
Petition 870190071668, of 7/26/2019, p. 31/67 / 41 were dispersed in distilled water and then applied to an aluminum support attached to a copper strip before the water evaporated.
[00065] Furthermore, the specific surface of the synthetic amorphous silicon dioxide was determined using gas absorption measurements (BET method) according to DIN 66131. The specific surface of the synthetic amorphous SiO2 is between 1 and 200 m ² / g , particularly between 1 and 50 m ² / g, in particular preferably between 1 and 30 m ² / g. Optionally, the products can also be mixed, for example, to selectively obtain mixtures with certain particle size distributions.
[00066] The purity of amorphous SiO2 can vary widely, depending on the production method and the producer. Suitable types were considered to be those containing at least 85% by weight of SiO2, preferably at least 90% by weight and in particular preferably at least 95% by weight.
[00067] Depending on the use and the desired strength, between 0.1% by weight and 2% by weight of the amorphous particulate SiO2 is used, preferably 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 mold base material.
[00068] The ratio of soluble glass binder to particulate metal oxide and amorphous SiO2 if present can be varied within wide limits. This provides the advantage of greatly improving the initial resistances of the taps, that is, the resistance immediately after removal of the tool, without substantially affecting the final resistances.
[00069] This is of great interest especially in light metal casting. On the one hand, high initial resistances are desired in order to be able to transport the taps or combine them in total tap packs without problems immediately after their production and, on the other hand, the final taps should not be too high in order to avoid problems during the disintegration of the tap after the leak, that is, the base material
Petition 870190071668, of 7/26/2019, p. 32/67 / 41 of the mold must be able to be removed from the cavities of the casting mold without problems immediately after casting.
[00070] Based on the weight of the binder (including diluent and solvent), amorphous SiO2 is preferably present at a fraction of 2 to 60% by weight, in particular preferably from 3 to 55% by weight and in particular preferably between 4 and 50% by weight, or in particular preferably based on the solids glass solids to amorphous SiO2 ratio of 10: 1 to 1: 1.2 (parts by weight).
[00071] The addition of amorphous SiO2 according to EP 1802409 B1 can occur both before and after the addition of binder, directly in the refractory material, but also, as described in EP 1884300 A1 (= US 2008/029240 A1), first one Premixing of SiO2 with at least part of the binder or sodium hydroxide can be produced and this can then be mixed into the refractory material. The binder or fraction of binder that may still be present and that was not used for the premix can be added to the refractory material before or after the addition of the premix, or together with it. Preferably, amorphous SiO2 is added to the refractory material before adding the binder.
[00072] In an additional embodiment, barium sulphate can be added to the mixture of mold material (DE 102012104934) to further improve the surface of the casting. Barium sulfate can be barium sulfate synthetically produced, as well as natural, that is, it can be added in the form of minerals containing barium sulfate, such as heavy spar or barite. Barium sulfate synthetically produced (also called Blanc Fixe) is produced, for example, with the help of a precipitation reaction.
[00073] For this purpose, normally soluble barium compounds (barium salts) are dissolved in water. Then the poorly soluble barium sulphate is precipitated by the addition of soluble sulphate salts (for example,
Petition 870190071668, of 7/26/2019, p. 33/67 / 41 sodium sulfate) or sulfuric acid. The precipitated barium sulfate is filtered, dried and possibly ground.
[00074] Natural barium sulphate is obtained as the raw ore and then processed by various methods (for example, classification by density, grinding, etc.). Preferably, the barium sulfate has a purity of more than 85% by weight, in particular preferably more than 90% by weight. The naturally obtained barium sulfate can, for example, contain calcium fluoride as a contaminant. The calcium fluoride fraction can typically be about 5% based on the total weight of natural barium sulfate.
[00075] The average particle size of the barium sulfate to be used according to the invention is preferably between 0.1 pm and 90 pm. The particle size distribution can be determined, for example, using dynamic light scattering (for example, Horiba LA 950).
[00076] Preferably, the classification residue on a sieve with a mesh size of 45 pm is less than 20% by weight, in particular preferably less than 10% by weight, in particular preferably less than 5% by weight. The classification residue is determined by sieve analysis according to DIN 66165 (Part 2) using a machine classification method, in which, according to one modality, no classification aids are used and, according to another modality , a chain ring is additionally used as a screening aid.
[00077] 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 preferably 0.1 to 2.0% by weight or 0.3 to 0.99% by weight, in each case based on the total mold material mixture. [00078] According to an additional modality, other substances characterized by low wetting with molten aluminum can be
Petition 870190071668, of 7/26/2019, p. 34/67 / 41 added to the mold material mixture according to the invention, for example, boron nitride.
[00079] A mixture of substances like this with low wettability, containing barium sulphate, among other substances, as a low wettability agent, can similarly lead to a smooth melt surface free of sand adhesion. Based on the total amount of substances with little or no wettability, the fraction of barium sulfate should be greater than 5% by weight, preferably greater than 10% by weight, in particular preferably more than 20% by weight or greater than 60% in weight. The upper limit is pure barium sulfate; in this case, the fraction of barium sulphates in non-wettable substances is 100% by weight. The mixture of substances with little or no wettability 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 preferably 0.1 to 2, 0% by weight or 0.3 to 0.99% by weight, in each case based on the mixture of mold material.
[00080] In a further embodiment, the mixture of mold material according to the invention may comprise a phosphorus-containing compound. This addition is preferred in the case of very thin wall sections of a casting mold. It preferably comprises inorganic phosphorus compounds, in which the phosphorus is preferably present in the +5 oxidation state. By adding phosphorus-containing compounds, the stability of the casting mold can be further increased. This is particularly important when the liquid metal collides on an inclined surface during metal casting and has a high erosive effect due to the high metallostatic pressure or can lead to deformations particularly in thin wall sections of the casting mold.
[00081] The phosphorus-containing compound is preferably present in the form of a phosphate or phosphorus oxide. Phosphate can be present as
Petition 870190071668, of 7/26/2019, p. 35/67 / 41 an alkali or alkaline earth metal phosphate, where alkali metal phosphates and especially the sodium salts thereof are preferred.
[00082] Theoretically, ammonium phosphates or phosphates of other metal ions can also be used. The alkaline or alkaline earth metal phosphates cited as preferred, however, are readily available in any desired quantity at a reasonable cost.
[00083] Phosphates of higher valence metal ions, particularly trivalent metal ions, are not preferred. It has been observed that when such higher valence metal ion phosphates, particularly trivalent metal ions, are used, the processing time of the mold material mixture is reduced. If the phosphorus-containing compound from the mold material mixture is added in the form of a phosphorus oxide, the phosphorus oxide is preferably in the form of phosphorus pentoxide. However, phosphorus trioxide and phosphorus tetroxide may also be used.
[00084] Orthophosphates, as well as polyphosphates, pyrophosphates or metaphosphates, can also be used as phosphates. Phosphates can, for example, be produced by neutralizing the corresponding acids with a corresponding base, for example, an alkali metal base, such as NaOH, or optionally also an alkaline earth metal base, where not all negative charges of the phosphate must be saturated with metal ions.
[00085] Metal phosphates as well as metal hydrogen phosphates and metal dihydrogen phosphates can be used, for example, Na3PO4, Na2HPO4, and NaH2PO4. Anhydrous phosphates as well as phosphate hydrates can be used. Phosphates can be introduced into the mold material mixture in crystalline or amorphous form.
[00086] Polyphosphates are particularly defined as linear phosphates that contain more than one phosphorus atom, in which phosphorus atoms are linked together by oxygen bridges. Polyphosphates are obtained
Petition 870190071668, of 7/26/2019, p. 36/67 / 41 by condensation of orthophosphate ions with water division, so that a linear chain of PO4 tetraedos connected to each other through their corners is obtained. Polyphosphates have the general formula (O (PO3) n) ^{(n + 2)} , where n corresponds to the chain length. A polyphosphate can comprise up to hundreds of PO4 tetraedos. 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 PO4 tetrahedra are bonded together in more than one of the corners and therefore exhibit polymerization in two or three dimensions.
[00087] Metaphosphates are defined as cyclic structures made up of PO4 tetrahedrons connected together by their corners. Metaphosphates have the general formula ((PO3) n) ^n- , where n is at least 3. Preferably n has values from 3 to 10.
[00088] Both phosphates and individual mixtures of various phosphates and / or phosphorus oxides can be used.
[00089] The preferred fraction of the phosphorus-containing compound, based on the base material of refractory mold, is between 0.05 and 1.0% by weight. At a fraction of less than 0.05% by weight, no definite effect is observed on the dimensional stability of the casting mold. If the phosphate fraction exceeds 1.0% by weight, the heat resistance of the casting mold decreases considerably. Preferably, the fraction of the phosphorus-containing compound is selected between 0.1 and 0.5% by weight.
[00090] The phosphorus-containing inorganic compound preferably contains between 40 and 90% by weight, in particular preferably between 50 and 80% by weight of phosphorus, calculated as P2O5. The phosphorus-containing compound itself can be added to the mold material mixture in solid or dissolved form. Preferably, the phosphorus-containing compound is added to the mold material mixture as a solid. If the compound containing
Petition 870190071668, of 7/26/2019, p. 37/67 / 41 phosphorus is added in the dissolved form, water is preferred as the solvent. It has been observed, as an additional advantage to the addition of a phosphorus-containing compound in the mold material mixtures to produce foundry molds, that the molds show very good disintegration after metal casting. This is true for metals that require lower casting temperatures, such as light metals, particularly aluminum. In the case of iron casting, temperatures above 1,200 ° C affect the casting mold, so that there is a greater risk of vitrification of the casting mold and thus deterioration of the characteristics.
[00091] In an additional embodiment, organic compounds (according to EP 1 802 409 B1 and WO 2008/046651) can be added to the mold material mixture according to the invention. The addition of small amounts of organic compounds can be advantageous for specific applications - for example, to regulate the thermal expansion of the cured mold material mixture. However, such an addition is not preferred, since this is again associated with CO2 emissions and other pyrolysis products.
[00092] Binders containing water in general have less fluidity, compared to binders based on organic solvents. This means that molding tools with narrow passages and multiple changes of directions cannot be filled equally. As a result, the males may have sections with inadequate compaction, which, in turn, can result in casting errors during casting. According to an advantageous embodiment, the mixture of mold material according to the invention contains a fraction of flake-type lubricants, particularly graphite or MoS2. Surprisingly, it has been observed that, by adding such lubricants, particularly graphite, even complex molds with thin wall sections can be produced, in which the casting molds continuously have a high density and uniform strength, so that
Petition 870190071668, of 7/26/2019, p. 38/67 / 41 essentially no casting defects were observed during casting. The amount of flake-type lubricant added, particularly graphite, preferably amounts to 0.05 to 1% by weight, in particular preferably 0.05 to 0.5% by weight, based on the mold base material.
[00093] Furthermore, surface active substances can be used, particularly surfactants, to improve the fluidity of the mold material mixture. Suitable representatives of these compounds are described, for example, in WO 2009/056320 (= US 2010/0326620 A1). In particular, surfactants with sulfate or sulfonate group (s) can be mentioned here.
[00094] An active surface substance is defined as a substance that can form a monomolecular layer on an aqueous surface, and thus, for example, is capable of forming a membrane. Furthermore, an active surface substance reduces the surface tension of water. Suitable active surface substances are, for example, silicone oils.
[00095] In particular preferably the surface active substance is a surfactant. Surfactants comprise a hydrophilic part (head) and a long hydrophobic part (tail) that are sufficiently balanced in their characteristics to the point that surfactants, for example, can form micelles in an aqueous phase or can become enriched at the interface.
[00096] Inherently, all classes of surfactants can be used in the mixing of mold material according to the invention. In addition to anionic surfactants, non-anionic surfactants, cationic surfactants and amphoteric surfactants can also be used.
[00097] Examples of nonionic surfactants are, for example, ethoxylated or propoxylated long chain alcohols, amines or
Petition 870190071668, of 7/26/2019, p. 39/67 / 41 acids, such as ethoxylated fatty alcohol, alkylphenol ethoxylates, grease amine ethoxylates, fatty acid ethoxylates, the corresponding propoxylates or sugar surfactants, for example, polyglycosides based on fatty alcohol. The fatty alcohols preferably comprise 8 to 20 carbon atoms. Suitable cationic surfactants are alkylammonium compounds and imidazoline compounds.
[00098] Preferably, anionic surfactants are used for mixing mold material according to the invention. As a polar hydrophilic group, the anionic surfactant preferably comprises a sulfate, sulfonate, phosphate or carboxylate group, in which sulfate and phosphate groups are particularly preferred. If anionic surfactants containing a sulfate group are used, preferably the monoesters of the sulfates are used. If phosphate groups are used as the polar group of the anionic surfactant, orthophosphoric acid mono and diesters are particularly preferred.
[00099] The surfactants used in the mold material mixture according to the invention have in common the fact that the non-polar hydrophobic part (tail) is preferably formed by alkyl, aryl and / or aralkyl groups which preferably comprise more than 6 carbon atoms, in particular preferably 8 to 20 carbon atoms. The hydrophobic part can have both straight chains and branched structures. Similarly, mixtures of various surfactants can be used. Particularly preferred anionic surfactants are selected from the group of oleyl sulphates, stearyl sulphate, palmitile sulphate, myristyl sulphate, lauryl sulphate, decyl sulphate, octyl sulphate, 2-ethylhexyl sulphate, 2-ethyloctyl sulphate 2-ethyldecyl, palmitoleyl sulphate, linolyl sulphate, lauryl sulphonate, 2-ethyldecyl sulphonate, palmityl sulphonate, stearyl sulphonate, 2-etilstearyl sulphonate, linoyl sulphonate, hexyl phosphate, 2-ethyl hexyl phosphate, caprine phosphate, lauryl phosphate, myristyl phosphate,
Petition 870190071668, of 7/26/2019, p. 40/67 / 41 palmitile phosphate, palmitoleyl phosphate, oleyl phosphate, stearyl phosphate, poly- (1,2-ethanedyl) -phenol hydroxyphosphate, poly- (1,2ethanedyl) -stearyl phosphate, and poly- (1,2-ethanedyl) -oleyl.
[000100] In the mold material mixture according to the invention, the pure active surface substance, based on the weight of the refractory mold base material, is preferably present in a fraction of 0.001 to 1% by weight, in particular preferably 0.01 to 0.2% by weight. Such surface-active substances are often sold commercially as 20% to 80% solutions. In this case, aqueous solutions of surface active substances are particularly preferred.
[000101] Basically, the active surface substance can be added to the mixture of mold material in the dissolved form, for example, in the binder, as a separate component or by means of a solid component that functions as a carrier material, for example, in an additive. In particular, preferably, the surface active substance is dissolved in the binder.
[000102] In addition to the mentioned constituents, the mixture of mold material according to the invention may comprise additional additives. For example, internal release agents can be added to facilitate detachment of casting molds from the molding tool. Suitable internal release agents are, for example, calcium stearate, fatty acid esters, waxes, natural resins or special alkyd resins.
[000103] Furthermore, silanes can also be added to the mold material mixture according to the invention to increase the stability of the molds and cores against high atmospheric humidity and / or against water-based mold coatings. According to a further preferred embodiment, the mold material mixture according to the invention contains a fraction of at least one silane. Suitable silanes are, for example, aminosilanes, epoxysilanes, mercaptosilanes, hydroxysilanes and
Petition 870190071668, of 7/26/2019, p. 41/67 / 41 of suitable silanes hydroxypropyltrimethoxysilane, mercaptopropyltrimethoxysilane, (3,4-epoxycyclohexyl) trimethoxysilane and N are
3ureidosilanes. Examples aminopropyltrimethoxysilane, ureidopropyltriethoxysilane, glycidyloxypropyltrimethoxysilane, (aminoethyl) -aminopropyltrimethoxysilane. Based on the binder, typically 0.1 to 2% by weight of silane is used, preferably 0.1 to 1% by weight. Additional suitable additives are alkali metal silicates, for example, potassium methyl silicate, of which 0.5 to 15% by weight, preferably 1 to 10% by weight and in particular preferably 1 to 5% by weight based on the binder can be used. If the mold material mixture contains silanes and / or methyl alkali silicates, they are usually added by incorporating into the binder beforehand. However, they can also be added to the impression material as separate components.
[000104] The mixture of mold material according to the invention represents an intensive mixing of at least the mentioned constituents. The particles of the base material of the refractory mold are preferably coated with a layer of the binder. Firm cohesion between the particles of the refractory mold base material can be achieved by evaporating the water present in the binder (about 40-70% by weight, based on the weight of the binder).
[000105] Despite the high strengths obtained with the binder system according to the invention, after casting, the foundry molds produced with the mixture of mold material according to the invention show surprisingly good disintegration, so that Mixing of mold material can easily be poured, even from constricted and angled sections of the casting mold again after casting. The molds produced from the mixture of mold material according to the invention are generally suitable for casting metals, for example light metals, non-ferrous metals or ferrous metals. However, the mixture of mold material according to the invention is especially suitable for
Petition 870190071668, of 07/26/2019, p. 42/67 / 41 smelting of ferrous metals.
[000106] The invention additionally relates to a method for producing casting molds for metal processing using the mixture of mold material according to the invention. The method according to the invention comprises the steps of:
• Prepare the mixture of mold material described above;
• Mold the mixture of mold material;
• Curing the mixture of molded mold material, whereby the cured casting mold is obtained.
[000107] In the production of the mixture of mold material according to the invention, in general, the procedure followed is that (for example, starting from a multi-component system) first the base material of refractory mold is taken and then the binder is added with agitation. In this process, soluble glass and particulate metal oxide according to the invention itself can be added in any desired order.
[000108] The additives described above can be added to the mold material mixture in any desired shape. 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 liquid component contains the soluble glass and optionally a surfactant (cf. above) and a second solid component comprises metal oxide according to the invention optionally together with one or more of the above-described components: synthetic amorphous silicon dioxide, carbohydrate, phosphate, a preferably flake-type lubricant and / or barium sulfate, particularly synthetic amorphous silicon dioxide.
[000109] The mixture of mold material is preferably prepared in the form of a multi-component system comprising at least the following components (A) and (B) and optionally (F), existing spatially separated from each other:
Petition 870190071668, of 7/26/2019, p. 43/67 / 41 (A) a pulverized additive component comprising at least one particulate metal oxide, wherein the particulate metal oxide comprises or consists of:
- at least one aluminum oxide in the alpha phase; and / or
- at least one mixed aluminum / silicon oxide, other than mixed aluminum / silicon oxide with layered silicate structure;
and
- no soluble glass;
(B) a liquid binder component (B) comprising at least:
- soluble glass containing water; and, optionally, (F) a fluid refractory component (F) comprising:
- a base material of refractory mold, and
- no soluble glass.
[000110] Each of the additional constituents of the components is defined in more detail below. Specifically, the additional constituents previously mentioned can preferably be associated with the following components (A), (B) and (F):
Component (A) (additive component): particulate amorphous SiO2, barium sulfate, phosphorus-containing compound (as a solid), organic compounds;
Component (B) (binder component): surfactants; phosphorus-containing compound (if soluble in water);
Component (F) (refractory component): synthetic mold materials.
[000111] Using the multi-component system, the mixture of mold material can be produced by combining the components in the required quantities or producing the component with the required quantities of the constituents defined more specifically in advance.
Petition 870190071668, of 7/26/2019, p. 44/67 / 41 [000112] In the production of the mold material mixture, the base material of refractory mold is placed in a mixer and then preferably the solid component (s) in the form of metal oxides first particulates, and optionally amorphous silicon dioxide, barium sulfate or additional pulverized solids are added and mixed with the base material of refractory mold.
[000113] The duration of the mixing is selected in such a way that there is an intimate mixing of the base material of refractory mold and added solid. The mixing duration depends on the amount of the mold material mixture to be prepared and the mixing apparatus used. Preferably, the duration of the mixture is chosen between 1 and 5 minutes.
[000114] Then, preferably with continued mixing of the mixture, the liquid 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 refractory mold base material. Here, too, the mixing duration depends on the amount of the mold material mixture to be produced and the mixing apparatus used. Preferably, the duration of the mixing process is selected between 1 and 5 minutes. A liquid component is defined as both a mixture of several liquid components and the totality of all individual liquid components, where these can also be added individually. Similarly, a solid component is defined as both the mixture of individual solid components and the totality of all the solid components described above, in which these can be added to the mixture of mold material individually, or one by one. According to another embodiment, the liquid component of the binder can first be added to the base material of the refractory mold and only then can the solid component be added to the mixture. According to an additional embodiment, first 0.05 to 0.3% water, based on the weight of the mold base material, is
Petition 870190071668, of 7/26/2019, p. 45/67 / 41 added to the base material of the refractory mold, and only then the solid and liquid components of the binder are added.
[000115] In this embodiment, a surprisingly positive effect on the processing time of the mold material mixture can be achieved. The inventors consider that the effect of water extraction from the solid component of the binder is reduced in this way, and the total curing process is correspondingly delayed. The mixture of mold material is then brought into the desired shape. In this process, the usual molding is used. For example, the mix of mold material can be applied to the molding tool with a tapping machine using compressed air. [000116] The mold material mixture is then fully cured, in which all known methods for soluble glass-based binders can be used, for example, hot curing, CO2 or air gasification or a combination of both and curing with liquid or solid catalysts.
[000117] In hot curing, water is extracted from the mixture of mold material. As a result, it is believed that condensation reactions are also initiated between silanol groups, so that soluble glasses cross-link.
[000118] For example, heating can take place in a molding tool, preferably with a temperature of 100 to 300 ° C, in particular preferably a temperature of 120 to 250 ° C. It is possible to cure the casting mold completely, even in the molding tool. However, it is also possible to cool only the outer areas of the casting mold, so that it has adequate strength to be removed from the molding tool. The casting mold can then be completely cured by extracting additional water. This can be done, for example, in an oven. Water extraction can also take place, for example, by extracting water under low pressure.
[000119] The cure of casting molds can be accelerated by blowing air
Petition 870190071668, of 7/26/2019, p. 46/67 / 41 heated in the molding tool. In this modality of the method, removal of the water contained in the binder is done, so that the casting mold is consolidated in periods of time suitable for industrial application. The temperature of the blown air is preferably 100 ° C to 180 ° C, in particular preferably 120 ° C to 150 ° C. The flow rate of the heated air is preferably adjusted in such a way that curing of the casting mold within suitable periods of time for industrial application is achieved. The time periods depend on the size of the foundry molds produced. Curing in less than 5 minutes, preferably less than 2 minutes, is desired. However, in the case of very large casting molds, longer periods of time may be necessary.
[000120] Removing water from the mold material mixture can also be accomplished by heating the mold material mixture by microwave irradiation.
[000121] Microwave irradiation is preferably done after the casting mold has been removed from the molding tool. For this purpose, however, the casting mold already has adequate strength. As previously explained, this can be achieved, for example, if at least one outer shell of the casting mold is already cured in the molding tool.
[000122] The methods according to the invention are inherently suitable for the production of all foundry molds customarily employed for metal casting, thus, for example, cores and molds. [000123] Foundry molds produced from the mixture of mold material according to the invention or the method according to the invention show high strength immediately after production, without the strength of the foundry molds after curing being so high that difficulties occur during the removal of the casting mold after the production of the casting. Furthermore, these foundry molds
Petition 870190071668, of 7/26/2019, p. 47/67 / 41 have high stability in the presence of high atmospheric humidity, that is, surprisingly the casting molds can also be stored without problems for long periods of time. As an advantage, the casting mold has a very high stability under mechanical loading, so that even thin-walled sections of the casting mold can be implemented without being deformed by the metallostatic pressure in the casting process. Thus, a further object of the invention is a casting mold which was obtained by the method described above according to the invention.
[000124] In the following, the invention will be explained on the basis of the examples, without being limited to them.
Examples
Effects of various powders containing aluminum oxide on bending strength and processing time [000125] To test a mixture of mold material, the so-called Georg Fischer test bars were produced. Georg Fischer's test bars are rectangular cross-section test bars with dimensions of 150 mm x 22.36 mm x 22.36 mm. The compositions of the mold material mixtures are shown 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 (Vogel & Schemmann AG, Hagen, DE). First, the quartz sand was placed in the mixer and the soluble glass was added with stirring. The soluble glass used was a sodium soluble glass that contained potassium fractions. In the following tables, therefore, the molar fraction is given as SiO2: M2O, where M is the sum of sodium and potassium. After the mixture was stirred for one minute, optionally amorphous SiO2 and / or barium sulfate was added while continuing to stir. The mixture was then stirred for another minute.
Petition 870190071668, of 7/26/2019, p. 48/67 / 41 • Mold material mixtures were transferred to the storage tank of a H 2.5 Hot-Box shot blasting machine from Roperwerk - GieBereimaschinen GmbH, Viersen, DE, whose molding tool was heated to 180 ° Ç.
• Mold material mixtures were introduced into the molding tool using compressed air (0.5 MPa (5 bar)) and remained in the molding tool for another 35 seconds.
• To accelerate the curing of mixtures, during the last 20 seconds, hot air (0.2 MPa (2 bar), 100 ° C at the tool inlet) was circulated in the molding tool.
• The impression tool has been opened and the test bars removed.
[000126] To determine the bending strength, the test bars were placed in a Georg Fischer resistance tester equipped with a 3-point bending device (DISA Industries AG, Schaffhausen, CH) and the force that causes the test bars break off was measured. The bending strengths were measured after the following plane:
• 10 seconds after removal (hot resistance) • 1 hour after removal (cold resistance) • 10 seconds after removal (hot resistance) of the mold material mixture stored for 1 h (without air exchange).
• 10 seconds after removal (hot resistance) of the mold material mixture stored for 2 h (without air exchange).
[000127] Comparison of the resistance to bending of mixtures 1.01 and 1.02 shows that both the resistance to hot and resistance to cold are increased by the addition of an amorphous SiO2 powder. This is in line with the prior art described in DE 102004042535 A1.
[000128] Comparison of mix 1.02 with mixtures 1.03 to 1.09 indicates
Petition 870190071668, of 7/26/2019, p. 49/67 / 41 clearly that powder containing aluminum oxide not according to the invention leads to worse resistances or reduces the processing time of the mold material mixture (cf. mixture resistance values 1.08). On the other hand, mixtures 1.10 to 1.13 show that powder containing aluminum oxide according to the inventions has little or no effect on resistances. The processing time (greater than 2 h) is also adequate.
Table 1
Compositions of mold material mixtures
H32 quartz sand Alkaline soluble glass Amor Amor Additive1.01 100 PBW 2.0 PBW ^a) - - Comparation 1.02 100 PBW 2.0 PBW ^a) 0.5 PBW ^b) - Comparation 1.03 100 PBW 2.0 PBW ^a) 0.5 PBW ^b) 0.5 PBW ^c) Comparation 1.04 100 PBW 2.0 PBW ^a) 0.5 PBW ^b) 0.5 PBW ^d) Comparation 1.05 100 PBW 2.0 PBW ^a) 0.5 PBW ^b) 0.5 PBW ^e) Comparation 1.06 100 PBW 2.0 PBW ^a) 0.5 PBW ^b) 0.5 PBW ^f) Comparation 1.07 100 PBW 2.0 PBW ^a) 0.5 PBW ^b) 0.5 PBW ^g) Comparation 1.08 100 PBW 2.0 PBW ^a) 0.5 PBW ^b) 0.5 PBW ^h) Comparation 1.09 100 PBW 2.0 PBW ^a) 0.5 PBW ^b) 0.5 PBW ^l) acc. invent according to the invention 1.10 100 PBW 2.0 PBW ^a) 0.5 PBW ^b) 0.5 PBW ^m) acc. invent according to the invention 1.11 100 PBW 2.0 PBW ^a) 0.5 PBW ^b) 0.5 PBW ⁿ⁾ acc. invent according to the invention 1.12 100 PBW 2.0 PBW ^a) 0.5 PBW ^b) 0.5 PBW ^o) acc. invent according to the invention
PBW = parts by weight; comparison = not according to the invention; acc. to invent. = according to the invention [000129] The envelopes in Table 1 have the following respective meanings:
a) Alkaline soluble glass with a SiO2: M2O fraction by weight of about 2.1, based on the total soluble glass, solids content of about 35%
b) GHL DL971W white microsilica (amorphous SiO2, silicon RW GmbH; formed during the metallurgical manufacture of silicon in an electric arc furnace)
c) AEROXIDE Alu 130 (fumed aluminum oxide with
Petition 870190071668, of 7/26/2019, p. 50/67 / 41 a BET surface area of 130 m2 / g; Evonik Industries AG)
d) AEROXIDE Alu 65 (pyrogenic aluminum oxide with a BET surface area of von 65 m2 / g; Evonik Industries AG)
e) ARGICAL-M 1000 (metacaolin, calc. kaolin, amorphous material consisting of lamellar particles, BET surface area of von 17 m2 / g; AGS Mineraux (IMERYS))
f) ARGICAL-M 1200S (metacaolin, calc. kaolin, amorphous material consisting of lamellar particles, BET surface area of 19 m2 / g; AGS Mineraux (IMERYS))
g) Ground Caolin FP 80 (BET surface area of 19 m2 / g; Dorfner)
h) ARGICAL C88 R (kaolinite, BET surface area of 13 m2 / g; AGS Mineraux (IMERYS))
l) Cyanite 100 Mesh (Cyanite Mining Corporation)
m) coarse ALODUR WDCF (special fumed silica dust, Treibacher Schleifmittel)
n) ALODUR FZM S (special zirconia mullite, Treibacher Schleifmittel)
o) ALODUR ZKSF (dust-like by-product of corundum production - zirconium, Treibacher Schleifmittel)
Table 2
Folding resistance
Hot resistance [N / cm ² ] Resistances after 1 h [N / cm ² ] Hot resistances (PT 1 h) [N / cm ² ] Hot resistance (PT 2 h) [N / cm ² ]1.01 90 410 - - Comparation 1.02 150 470 145 150 Comparation 1.03 55 200 Comparation 1.04 75 210 Comparation 1.05 115 310 Comparation 1.06 75 270 Comparation 1.07 105 250 Comparation 1.08 130 340 110 100 Comparation 1.09 150 465 150 140 acc. invent according to the invention 1.10 150 470 140 145 acc. to invent
Petition 870190071668, of 7/26/2019, p. 51/67 / 41
according to the invention 1.11 145 465 150 140 ace. invent according to the invention 1.12 165 460 160 165 ace. invent according to the invention
PT = processing time; - = nicht bestimmt; Comparison = not according to the invention; ace. to invent. = according to the invention
Improvement of the casting surface [000130] The effects of particulate metal oxides according to the invention on the casting surface were investigated. The following procedure was used:
• So-called staggered males were produced. Their shapes and dimensions are shown in Fig. 1 and 2. Fig. 1 shows a side view, specifying the height staggered in mm in the figure and the outside diameter of the staggerings to the right of this (first staggered diameter value, second diameter value staggered above). [000131] In Fig. 2, the stepped tap is shown at the top. The production of the stepped tap was done using a Hot-Box tapping machine, whose molding tool was heated to 180 ° C. The mold material mixture was introduced into the pressure molding tool and, to accelerate the hot cure, hot air was circulated through the mold material mixture using the mold material mixtures 1.02 and 1.09 to 1.12 in Table 1 were incorporated in a sand casting mold in such a way that only the underside of the widest stepped part (the standing surface of the pyramid core) does not come into contact with the molten metal during the casting process. The stepped taps are suspended in the casting mold, which is then filled with the liquid metal in such a way that the smaller stepped portion (smaller width) is the first to make contact with the liquid metal.
• The casting was carried out with a gray cast iron bath GG20 (new name: GJL20) at a casting temperature of about
Petition 870190071668, of 7/26/2019, p. 52/67 / 41 of 1,430 ° C and a casting height of 55 cm.
• After the casting mold has cooled, the casting was released from the sand by hitting it with a hammer.
• Castings were then evaluated for remaining sand adhesions, possible sintering / burning, and roughness. Ratings from 1 (very good) to 6 (inadequate) were assigned; these are shown in Table 3. The castings obtained are not yet free of sand adhesions; especially in areas with delicate core parts (staggered parts with small widths), sand adhesions can be observed and, therefore, the following procedure was employed.
• Then the castings were cleaned with a sandblasting device with a light sandblasting pressure of 1 bar. The shot used were glass microspheres with particle diameters between 100 and 200 gm.
[000132] The sandblasting time was limited to one minute. The conditions for sandblasting cleaning were selected in such a way that differences between the castings produced with different mixes of mold material could be visualized without substantially affecting the surface quality.
• The castings were then evaluated for possible sintering / burning and surface roughness. For this purpose, grades 1 (a) to 6 (inadequate) have been assigned; these are shown in Table 3.
Table 3
Surface quality assessment
Surface quality before sandblasting Surface quality after sandblasting1.02 5 4 Comparation 1.09 3 2 according to the invention 1.10 3 2 acc. to invent acc. invent according to
Petition 870190071668, of 7/26/2019, p. 53/67 / 41
invention 1.11 3 2 acc. invent according to the invention 1.12 2 1 acc. invent according to the invention
[000133] The melt section of mixture 1.02 clearly demonstrates more adhesion / burning of sand or roughness than the melt sections of mixtures 1.09 to 1.12. The positive effect of particulate metal oxides according to the invention on the casting surfaces is very clear here. Particularly advantageous results are obtained with the dust-like by-product of the production of corundum - zirconium. Therefore, the use of this substance is very particularly preferred.
The surface quality is distinctly improved by the use of sandblasting, since the adherence of sand residues can be removed completely - the surface is also slightly smoothed out through this use. However, great attention was paid to the blasting of all castings under the same conditions. Therefore, the differences are merely attributable to compositions of the mold material mixtures. It should also be noted that the so-called "flutes" can only be observed to a very small degree, or none at all, although quartz sand has been used as the base mold material.

权利要求:
Claims (26)
[1]
1. Mixing of mold material to produce molds and casting cores for metal processing, characterized by the fact that it comprises at least:
a) a base material of refractory mold;
b) soluble glass as an inorganic binder; and
c) at least one particulate metal oxide, wherein the particulate metal oxide comprises or consists of:
- at least one aluminum oxide in the alpha phase; and / or
- at least one mixed aluminum / silicon oxide without a layered silicate structure.
[2]
Mixture of mold material according to claim 1, characterized in that the particulate metal oxide additionally comprises a crystalline silicon oxide.
[3]
Mixture of mold material according to any one of the preceding claims, characterized by the fact that aluminum oxide in the alpha phase and mixed aluminum / silicon oxide, other than mixed aluminum / silicon oxides with a silicate structure in layers, is present between 0.05% by weight and 2.0% by weight, preferably between 0.1% by weight and 2.0% by weight, in particular preferably between 0.2% by weight and 0.8% by weight of the mold material mixture, in each case based on the mold base material.
[4]
Mixture of mold material according to any one of the preceding claims, characterized in that the particulate metal oxide comprises or consists of an aluminum oxide in the alpha phase.
[5]
Mixture of mold material according to any one of the preceding claims, characterized in that the particulate metal oxide comprises or consists of a mixed aluminum / silicon oxide,
Petition 870190118928, of 11/18/2019, p. 10/16
2/6 other than mixed aluminum / silicon oxides with layered silicate structure.
[6]
6. Mixing of mold material according to any one of the preceding claims, characterized by the fact that the mixed aluminum / silicon oxide, based on the sum of aluminum and silicon atoms, contains more than 50 to 99% atomic atoms aluminum, preferably more than 60 to 85% atomic.
[7]
Mixture of mold material according to any one of the preceding claims, characterized in that the particulate metal oxide comprises or consists of a nesosilicate, in particular it is a synthetic or natural mullite, or an element of the silimanite group, preferably cyanite and, independently of this, preferably additionally comprises zirconium oxide, either incorporated or as a separate phase.
[8]
8. Mixing of mold material according to any one of the preceding claims, characterized by the fact that the particulate metal oxide is or contains a corundum - zirconium and / or a zirconium mullite.
[9]
9. Mixing of mold material according to any one of the preceding claims, characterized by the fact that, in particulate metal oxide,
a) the fraction of aluminum oxide, calculated as AEO3, is:
- greater than 25% by weight;
- preferably greater than 25% by weight and less than 80% by weight;
- in particular preferably more than 30% by weight and less than 70% by weight;
- in particular preferably more than 40% by weight and less than 60% by weight;
b) preferably the fraction of zirconium oxide, calculated
Petition 870190118928, of 11/18/2019, p. 11/16
3/6 as ZrO ₂ , is:
- greater than 2% by weight of;
- preferably greater than 2% by weight and less than 50% by weight Weight;- in particular preferably greater than 4% by weight and less than 40% by weight; - in particular preferably greater than 8% by weight, and
less than 30% by weight; and regardless
c) the fraction of silicon oxide, calculated as SiO2, if present, is:
- greater than 5% by weight;
- preferably greater than 5% by weight and less than 60% by weight;
- in particular preferably more than 15% by weight and less than 50% by weight;
- in particular preferably more than 20% by weight and less than 45% by weight;
and regardless
d) preferably the fraction of other metals calculated as their oxides in the main oxidation states, particularly Fe2O3, Na2O TiO2, MgO and CaO, is less than 12% by weight, preferably less than 8% by weight and in particular preferably less than 4 % by weight.
[10]
10. Mold material mixture according to any one of the preceding claims, characterized by the fact that the particulate metal oxide is a dust containing aluminum oxide and dust containing zirconium oxide that can be obtained as a by-product in the production of zirconium corundum .
[11]
11. Mixing of mold material according to any of the preceding claims, characterized by the fact that the surface
Petition 870190118928, of 11/18/2019, p. 12/16
4/6 specific mixed oxide is less than 50 m ² / g, preferably less than 30 m ² / g, in particular preferably less than 17 m ² / g and regardless of this it is greater than 0.1 m ² / g, preferably greater than 0.5 m ² / g, in particular preferably greater than 1 m ² / g.
[12]
Mixture of mold material according to any one of the preceding claims, characterized by the fact that the average primary particle size determined as the diameter of particulate metal oxide (s) is between 0.01 qm and 50 qm, particularly between 0.02 qm and 20 qm, in particular preferably between 0.02 qm and 10 qm.
[13]
13. Mixing of mold material according to any one of the preceding claims, characterized by the fact that the residue from sieving particulate metal oxide through a sieve with a mesh size of 75 qm (200 mesh) is no more than about 50% by weight, preferably not more than about 30% by weight, more preferably not more than about 20% by weight and in particular preferably not more than about 15% by weight.
[14]
14. Mixing of mold material according to any one of the preceding claims, characterized by the fact that the average ratio of the largest longitudinal dimension to the smallest longitudinal dimension for all spatial directions of the respective particulate metal oxide particle is preferably less than 10: 1, in particular preferably less than 5: 1 and in particular preferably less than 3: 1 and in particular preferably less than 1.1: 1.
[15]
Mixture of mold material according to any one of the preceding claims, characterized in that the particulate metal oxide is used as a fluid fluid powder in the mixture of mold material.
[16]
16. Mixing of mold material according to any one of the preceding claims, characterized by the fact that the mixture of
Petition 870190118928, of 11/18/2019, p. 13/16
5/6 mold material contains a maximum of 1% by weight, preferably a maximum of 0.2% by weight of organic compounds.
[17]
Mixture of mold material according to any one of the preceding claims, characterized in that the mixture of mold material further comprises barium sulphate, preferably in an amount of 0.02 to 5.0% by weight, in in particular preferably 0.1 to 2.0% by weight, in each case based on the mixture of total mold material.
[18]
18. Mixing of mold material according to any one of the preceding claims, characterized in that the soluble glass has a molar fraction SiO2 / M2O of 1.6 to 4.0, preferably 2.0 to less than 3.5 , with M equal to the sum of lithium, sodium and potassium.
[19]
19. Mold material mixture according to any of the preceding claims, characterized in that the mold material mixture contains 0.5 to 5% by weight of soluble glass, preferably 1 to 3.5% by weight of soluble glass, based on the mold base material, where the solids fraction of the soluble glass reaches 25 to 65% by weight, preferably 30 to 60% by weight.
[20]
20. Mixture of mold material according to any one of the preceding claims, characterized in that the mixture of mold material additionally comprises surfactants, preferably selected from the group of anionic surfactants, particularly those with a sulfonic acid or sulfonate group. , particularly in each case in a fraction of 0.001 to 1% by weight, in particular preferably 0.01 to 0.2% by weight, based on the weight of the refractory mold base material.
[21]
21. Mold material mixture according to any one of the preceding claims, characterized in that the mold material mixture additionally comprises graphite, preferably of graphite.
Petition 870190118928, of 11/18/2019, p. 14/16
6/6
0.05 to 1% by weight, particularly 0.05 to 0.5% by weight, based on the weight of the refractory mold base material.
[22]
22. Mold material mixture according to any one of the preceding claims, characterized in that the mold material mixture additionally comprises at least one phosphorus-containing compound, preferably between 0.05 and 1.0% by weight, in particularly preferably 0.1 and 0.5% by weight, based on the weight of the base materials of refractory molds.
[23]
23. Mold material mixture according to claim 1, characterized in that it additionally comprises hollow microspheres, particularly hollow microspheres of aluminum silicate and / or hollow borosilicate microspheres for smelting ferrous metals or aluminum.
[24]
24. Method for producing foundry molds or cores, characterized by the fact that it comprises:
• supplying the mold material mixture as defined in any one of claims 1 to 22, • introducing the mold material mixture into a mold, and • curing the mold material mixture.
[25]
25. Method according to claim 24, characterized in that the mixture of mold material is introduced into the mold with a blasting machine using compressed air and the mold is a molding tool and the molding tool has a or more gases circulating through it, particularly CO2 or gases containing CO2.
[26]
26. Method according to claim 24 or 25, characterized in that, for curing, the mixture of mold material is exposed to a temperature of at least 100 ° C, preferably for less than 5 min.

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法律状态:
2018-11-21| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2019-04-30| B07A| Technical examination (opinion): publication of technical examination (opinion)|

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2019-08-20| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|

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2019-12-17| B09A| Decision: intention to grant|

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2020-01-28| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 20/12/2013, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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DE102012113073.6A|DE102012113073A1|2012-12-22|2012-12-22|Molding mixtures containing aluminum oxides and / or aluminum / silicon mixed oxides in particulate form|

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PCT/DE2013/000813|WO2014094721A2|2012-12-22|2013-12-20|Mold material mixtures containing metal oxides of aluminum and zirconium in particulate form|

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