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    • 专利摘要:
    The invention refers to mixtures of mold material based on inorganic binders, to produce molds and cores for metal molding. said mixtures consist of at least one refractory mold base material, an inorganic binder and amorphous silicon dioxide as an additive. the invention also relates to a method for producing molds and cores using said mold material mixtures.
    公开号:BR112015008549B1
    申请号:R112015008549-0
    申请日:2013-10-18
    公开日:2019-11-19
    发明作者:Gieniec Antoni；Wallenhorst Carolin；bartels Dennis；Koch Diether；Lincke Hannes；Deters Heinz；Oberleiter Martin；Schmidt Oliver
    申请人:Ask Chemicals Gmbh；
    IPC主号:
    专利说明:

    “MOLD MATERIAL MIXTURE, METHOD TO PRODUCE CASTING MACHES OR MOLDS, MOLD OR MALE, AND USE OF A MOLD MATERIAL MIXTURE” [001] The invention relates to a mixture of mold material based on inorganic binders for produce molds and cores for metal casting, consisting of at least one basic refractory mold material, an inorganic binder and particulate amorphous silicon dioxide as an additive. The invention also relates to a method for producing molds and cores using said molded material mixtures.
    Prior Art [002] Foundry molds are composed essentially of molds or molds and cores that represent the negative shapes of the castings to be produced. Said taps and molds consist of a refractory material, for example, quartz sand, and a suitable binder that provides adequate mechanical resistance to the casting following the removal of the mold. The refractory mold base material is preferably present in a free-flowing form, so that it can be packaged into a suitable mold cavity and compressed therein. The binder produces firm cohesion between the particles of the mold base material, so that the cast mold achieves the necessary mechanical stability.
    [003] In casting, molds from the outer walls for casting, and cores are used to produce cavities within the casting. It is not absolutely necessary that the molds and cores are made of the same material. For example, in cold casting, the conformation of the external area of the casting is formed using permanent metal molds. A combination of molds and cores produced from mold mixtures of different compositions and using different methods is also possible. If only the term "molds" is used in the sequence for the sake of simplicity, the statements apply equally to males as well as / 37 which are based on the same mold mixture and produced according to the same method.
    [004] Molds can be produced using both organic and inorganic binders that can be cured by both cold and hot methods in each case.
    [005] The cold method is the name applied to methods that are carried out essentially without heating the modeling tool, usually at room temperature or at an appropriate temperature to produce a reaction if desired. For example, curing is performed by the fact that the gas is passed through the mixture of mold material to be cured and produces a chemical reaction at this point. In hot methods the mixture of mold material, after molding, for example, is heated by the hot molding tool to a temperature high enough to expel the solvent present in the binder and / or to initiate a chemical reaction to cure the binder .
    [006] Because of their technical characteristics, organic binders have great financial significance in the market today. Regardless of their composition, however, they have the disadvantage of decomposing during casting, thereby emitting considerable amounts of hazardous materials such as benzene, toluene and xylenes. In addition, the casting of organic binders generally leads to odor and smoke disturbances. In some systems, dangerous emissions even occur during the manufacture and / or storage of taps. Even though emissions are gradually reduced over the years by the development of the binder, they cannot be completely avoided with organic binders. For this reason, in recent years research and development activity is again turning to inorganic binders in order to improve the same and the product properties of the molds and cores produced with them.
    [007] Inorganic binders are known, especially those / 37 based on water-soluble glasses. They found their greatest use during the 1950s and 1960s, but they quickly lost their significance with the emergence of modern organic binders. Three different methods are available to cure water-soluble glasses:
    -pass a gas, for example, CO2, air or a combination of the two, through it,
    -add liquid or solid curing agents, for example, esters
    - thermal curing, for example, in the hot box method or by microwave treatment.
    [008] CO2 curing is described, for example, in GB 634817; curing with hot air without added CO2, for example, in H. Polzin, W. Tilch and T. Kooyers, Giesserei-Praxis 6/2006, p. 171. Further development of CO2 curing for subsequent air discharge is disclosed in DE 102012103705.1. Ester curing is known, for example, from GB 1029057 (called the non-cooking method).
    [009] Thermal curing of water-soluble glass is discussed, for example, in US 4226277 and EP 1802409, in which in the latter case particulate synthetic amorphous SiO2 is added to the mold material mixture to increase strength.
    [0010] Other known inorganic binders are based on phosphates and / or a combination of silicates and phosphates, where curing is carried out in the same way according to the methods mentioned above. The sequence can be mentioned in this connection as examples: US 5,641,015 (phosphate binders, thermal cure), US 6,139,619 (silicates / phosphate binders, thermal cure), US 2,895,838 (silicate / phosphate binders, cure with CO2), and US 6,299,677 (silicate / phosphate binders, ester curing).
    [0011] In the patents and applications cited EP 1802409 and DE
    102012103705.1 it is suggested that amorphous silica be added to each / 37 of the mold material mixtures. The S1O2 has the task of improving the rupture of taps after exposure to heat, for example, after casting. EP 1802409 B1 and DE 102012103705.1 extensively illustrate that the addition of synthetic particulate amorphous SiO2 generates a distinct increase in strength.
    [0012] It is suggested in EP 2014392 B1 that a spherical amorphous SiO2 suspension be added to the mixture of mold material, consisting of mold material, sodium hydroxide, binder based on alkaline silicate and additives, where SiO2 should be present in two particle size classes. In this way good flow capacity, high resistance to bending and a high cure speed can be obtained. Problem statement [0013] The purpose of the present invention is to further improve the properties of inorganic binders, to make them more universally useful, and to help them become an even better alternative to today's dominant organic binders.
    [0014] In particular it is desirable to provide mixtures of mold material that can make it possible to produce cores with more complex geometry based on additionally improved resistances and / or improved compaction, or in the case of simpler core geometries, to reduce the amount of binder and / or shorten curing times.
    Summary of the invention [0015] This objective is achieved by mixtures of mold material with the functionalities of the independent claims. Advantageous further developments form the subject of the dependent claims and will be described below.
    [0016] Surprisingly it was discovered that among the amorphous silicon dioxides which are types which differ in a different way from the others in terms of their effect as an additive to the binder. If the additive is / 37
    Added amorphous particulate S1O2 that was produced by the thermal decomposition of ZrSiO4 to form ZrO 2 and SiO 2 , followed by essentially complete or partial removal of ZrO 2 , it is observed that with the addition of the same amount and under identical reaction conditions, surprising improvements large in strength are obtained and / or the core weight is greater than how much particulate amorphous SiO2 from other production processes mentioned in EP 1802409 B1 is used. The increase in core weight in identical external dimensions of the core is accompanied by a decrease in gas permeability, indicative of greater packaging of the mold material particles.
    [0017] The amorphous particulate SiO2 produced according to the above method is also known as "synthetic amorphous S1O2" The amorphous particulate S1O2 can be described for production according to the following parameters, either cumulatively or alternatively.
    [0018] The mixture of mold material according to the invention contains at least:
    -a base material of refractory mold,
    -an inorganic binder, preferably based on water-soluble glass, phosphate or a mixture of the two,
    -an additive consisting of amorphous particulate SiO2, in which this is obtained by thermal decomposition of ZrSiO4 to form ZrO2 and SiO2. Detailed description of the invention [0019] The general procedure followed in the production of a mixture of mold material is that the mixture of base material of refractory mold is taken initially and then the binder and additive are added, together or one after the another, while stirring. Naturally, it is also possible to first add the components completely or partially, together or separately and shake them during or after the addition. Preferably the binder is introduced before the additive. It is agitated until the binder is evenly distributed and the additive in the mold base material is guaranteed.
    [0020] The mold base material is then placed in the desired shape. In this process, customary molding methods are used. For example, the mix of mold material can be fired into the modeling tool with compressed air using a tapping machine. An additional possibility is to allow mixing of mold material to flow freely from the mixer to the modeling tool and compact it by shaking, stamping or pressing.
    [0021] The curing of the mold material mixture is carried out in an embodiment of the invention using the Hot Box process, that is, it is cured with the aid of hot tools. Hot tools preferably have a temperature of 120 ° C, particularly preferably 120 ° C to 250 ° C. Preferably in this process a gas (such as CO2 or CO2 enriched air) is passed through the mold mixture, where this gas preferably has a temperature of 100 to 180 ° C, particularly preferably 120 to 150 ° C, as described in EP 1802409 B1. The above process (Hot Box process) is preferably performed on a tapping machine.
    [0022] Regardless of this, curing can also be carried out by the fact that CO2, a mixture of CO2 / gas (for example, air) or CO2 and a gas / mixture of gas (for example, air) are passed in sequence ( as described in detail in DE 102012103705) through the cold molding tool or through the mixture of mold material contained therein, where the term "cold" means temperatures of less than 100 ° C, preferably less than 50 ° C and especially room temperature (eg 23 ° C). The gas or gas mixture passed through the modeling tool or through the mold material / 37 mixture can preferably be slightly heated, for example, to a temperature of 120 ° C, preferably to 100 ° C, particularly preferably to 80 ° Ç.
    [0023] Last but not least, as an alternative to the two methods mentioned above it is also possible to mix a solid or liquid curing agent with the mixture of mold material before molding, and then this will produce the curing reaction.
    [0024] Common materials can be used as refractory mold base materials (simply called mold base materials in the sequence) for the production of foundry molds. Suitable materials, for example, are quartz, zirconia or chromium sand, olivine, vermiculite, bauxite and refractory clay. In this process it is not necessary to use the new sand exclusively. In order to conserve resources and avoid disposal costs, it is still advantageous to use the widest possible fraction of old regenerated sand.
    [0025] For example, a suitable sand is described in WO 2008/101668 (= US 2010/173767 A1). Regenerated materials obtained by washing and then drying are also suitable. Regenerates obtained by purely mechanical treatment can also be used. As a rule, regenerates can make up at least 70% by weight of the base mold material, preferably at least about 80% by weight and particularly preferably at least about 90% by weight.
    [0026] As a rule, the average diameter of the mold base material is between 100 pm and 600 pm, preferably between 120 pm and 550 pm and particularly preferably between 150 pm and 500 pm. The particle size can be determined, for example, by screening according to DIN 66165 (part 2).
    [0027] In addition, synthetic mold materials can also be used as mold base materials, especially as additives for common mold base materials, but also as the exclusive mold base material, such as beads glass, glass granules, the spherical ceramic mold base materials known under the name "Cerabeads" or "Carboaccucast" or micro-hollow aluminum silicate beads (so-called microspheres). Such aluminum silicate micro-hollow beads are sold, for example, Poe Omega Minerals Germany GmbH, Norderstedt, under the name "Omega-Spheres." Corresponding products are also available from PQ Corporation (USA) under the name " Extendospheres. ”[0028] It has been discovered in aluminum casting experiments that when synthetic mold base materials are used, for example, in the case of glass beads, glass granules or microspheres, less mold sand remains adhered to the surface of metal after casting that how much pure quartz sand is used. The use of synthetic mold base materials therefore makes it possible to produce smoother molding surfaces, so that laborious post-blasting treatment is not necessary, or at least is necessary to a less considerable degree.
    [0029] It is not necessary for the mold base material to be made entirely of synthetic mold base materials. The preferred fraction of the synthetic mold base materials is at least about 3% by weight, particularly preferably at least 5% by weight, especially preferably at least about 10% by weight, preferably at least about 15% by weight, particularly preferably at least about 20% by weight, in each case based on the total amount of the refractory mold base material.
    [0030] As an additional component the mixture of mold material according to the invention comprises an inorganic binder, for example, based on water-soluble glass. The water-soluble glasses used in this case can be conventional water-soluble glasses such as those used previously as binders in mixtures of mold material.
    [0031] These water-soluble glasses contain dissolved alkaline silicates and can be produced by dissolving the glass-like lithium, sodium and potassium silicates in water.
    [0032] Water-soluble glasses preferably have a molar module of SiO 2 / M2O in the range of 1.6 to 4.0, especially 2.0 to less than 3.5, where M represents lithium, sodium or potassium . The binder can also be based on water-soluble glasses that contain more than one of the alkaline ions mentioned, for example, the lithium-modified water-soluble glasses known from DE 2652421 A1 (= GB 1532847). In addition, water-soluble glasses can also contain multivalent ions such as boron or aluminum (corresponding products are described, for example, in EP 2305603 A1 (= WO2011 / 042132 A1).
    [0033] Water-soluble glasses have a fraction of solids in the range of 25 to 65% by weight, preferably 30 to 60% by weight. The solids fraction refers to the amount of SiO2 and M2O contained in the water-soluble glass.
    [0034] Depending on the use and the desired resistance level, between 0.5% by weight and 5% by weight of the binder based on water soluble glass is used, preferably between 0.75% by weight and 4% by weight , particularly preferably between 1% by weight and 3.5% by weight, in each case based on the mold base material. The reported weight% is based on water soluble glasses with a fraction of solids as mentioned above, that is, it includes the diluent.
    [0035] Instead of water-soluble glass binders, those based on water-soluble phosphate glasses and / or borates can also be used, for example, as described in US 5,641,015.
    [0036] Preferred phosphate glasses have a solubility in / 37 water of at least 200 g / L, preferably at least 800 g / L and contain between 30 and 80 mol% of P 2 O5, between 20 and 70% in mol of Li 2 O, Na 2 O or K2O, between 0 and 30 mol% of CaO, MgO or ZnO and between 0 and 15 mol% of Al2O3, Fe2O3 or B2O3. The particularly preferred composition is 58 to 72% by weight of P2O5, 28 to 42% by weight of Na2O and 0 to 16% by weight of CaO. The phosphate anions are preferably present in the phosphate glasses in the form of chains.
    [0037] Phosphate glasses are commonly used as aqueous solutions of about 15 to 65% by weight, preferably about 25 to 60% by weight. However, it is possible to add the phosphate glass and water separately to the mold base material, in which at least part of the phosphate glass dissolves in the water during the production of the mold mixture.
    [0038] Typical addition amounts for phosphate glass solutions are from 0.5% by weight to 15% by weight, preferably between 0.75% by weight and 12% by weight, particularly preferably between 1% by weight and 10% by weight, in each case based on the mold base material. The content declaration in each case is based on phosphate glass solutions with a fraction of solids as indicated above, that is, including the diluent.
    [0039] In the case of curing according to the so-called non-cooking method, mixtures of mold material preferably also contain curing agents that generate consolidation of the mixtures without the addition of heat or the need to pass a gas through the mixture. These curing agents can be liquid or solid, organic or inorganic in nature.
    Suitable organic curing agents, for example, are carboxylic acid esters such as propylene carbonate, carboxylic mono acid esters with 1 to 8 carbon atoms with monofunctional, bifunctional or trifunctional alcohols such as ethylene glycol diacetate, glycerol esters of acid monoacetic, biacetic or triacetic, as well as / 37 as cyclic hydroxycarboxylic acid esters, for example, γ-butyrolactone. The esters can be used in a mixture with each other.
    [0041] Organic curing agents suitable for binders based on water-soluble glass are, for example, phosphates, such as Lithopix P26 (an aluminum phosphate from Zschimmer and Schwarz GmbH & Co KG Chemische Fabriken) or Fabutit 748 (a phosphate from Chemische Fabrik Budenheim KG).
    [0042] The ratio of curing agent to binder can vary depending on the desired characteristic, for example, processing time and / or extraction time of mixtures of mold material. Advantageously the curing agent fraction (weight ratio of curing agent to binder and, in the case of water-soluble glass, the total weight of the silicate solution or other binders incorporated in solvents) is greater than or equal to 5% by weight, preferably greater than or equal to 8% by weight, particularly preferably greater than or equal to 10% by weight, in each case based on the binder. The upper limits are less than or equal to 25% by weight based on the binder, preferably less than or equal to 20% by weight, particularly preferably less than or equal to 15% by weight.
    [0043] Mold material mixtures contain a fraction of a particulate amorphous SiO2 produced in a synthetic way, in which it originates from the thermal degradation process from ZrSiO4 to ZrO 2 and SiO 2 .
    [0044] Corresponding products are sold, for example, by the companies Possehl Erzkontor GmbH, Doral Fused Materials Pty. Ltd., Cofermin Rohstoffe GmbH & Co. KG and TAM Ceramics LLC (ZrSiO4 process).
    [0045] Surprisingly, it was discovered that particulate amorphous SiO2 produced in a synthetic manner according to this method, assuming identical added quantities and reaction conditions, provides the males with greater resistance and / or a higher male weight than amorphous S1O2 from other manufacturing processes, for example, production of silicon or ferrosilicon, hydrolysis by SiCl4 flame or a precipitation reaction. The mold material mixtures according to the invention thus have improved flowability and therefore can be compacted more extensively at the same pressure.
    Both have positive effects on the utilization properties of the mold material mixtures, since the males with more complex geometries and / or smaller wall thicknesses can be produced in this way if compared to previously. In the case of simple taps without greater demands imposed on the resistances, on the other hand, it is possible to reduce the binder content and thus increase the process savings. The improved compression of the mold material mixture implies one more advantage in that the particles of the mold material mixture have a closer connection than in the prior art, so that the core surface is more free of pore, which leads to reduced surface roughness in the casting.
    [0046] Without wishing to be bound by this theory, the inventors assume that the improved flowability is based on the fact that the amorphous particulate SiO2 used according to the invention has a lower tendency to agglomerate than the amorphous SiO2 from other manufacturing processes, and therefore more primary particles are already present even without the action of greater shear forces. In Fig. 1 it can be seen that more individual particles are present in SiO2 according to the invention than in the comparison preparation (Fig. 2). In Fig. 2 it is also possible to identify a greater degree of coalescence of individual spheres in larger conglomerates, which can no longer be broken down into the primary particles. In addition, the two figures indicate that the primary SiO2 particles according to the invention have a larger particle size distribution / 37 than in the prior art, which in the same way can contribute to the improved flow capacity.
    [0047] The particle size was determined by dynamic light scattering on a Horiba LA 950, and the scanning electron photomicrographs were recorded using an ultra high resolution scanning electron microscope, Nova NanoSem 230 FEI equipped with a Lens Detector Through (TLD). For SEM measurements, the samples were dispersed in distilled water and then applied to an aluminum retainer covered with a copper strip before the water was evaporated. In this way details of the primary particle shape can be viewed in the order of magnitude of 0.01 pm.
    [0048] Because of the way it is made, the amorphous SiO 2 that originates from the ZrSiO4 process can still contain zirconium compounds, especially ZrO2. The zirconium content, calculated as ZrO2, is commonly less than about 12% by weight, preferably less than about 10% by weight, particularly preferably less than about 8% by weight, and especially preferably less than about 5% by weight, and on the other hand greater than 0.01% by weight, greater than 0.1% by weight or even greater than 0.2% by weight.
    [0049] In addition, for example, Fe2O3, Al2O3, P2O5, HfO2, TiO2, CaO, Na2O and K2O can be used with a total content of less than about 8% by weight, preferably less than about 5% by weight and particularly preferably less than about 3% by weight.
    [0050] The water content of the particulate amorphous SiO2 used according to the invention is less than 10% by weight, preferably less than 5% by weight and particularly preferably less than 2% by weight. In particular, amorphous SiO 2 is used as a free-flowing dry powder. The powder is free flowing and is suitable for pouring under its own weight.
    / 37 [0051] The average particle size of particulate amorphous S1O2 preferably ranges between 0.05 pm and 10 pm, especially between 0.1 pm and 5 pm and particularly preferably between 0.1 pm and 2 pm, where primary particles diameters between 0.01 pm and about 5 pm were found by SEM. The determination was made using dynamic light scattering on a Horiba LA 950.
    [0052] Particulate amorphous silicon dioxide has an average particle size of advantageously less than 300 pm, preferably less than 200 pm, particularly preferably less than 100 pm. The particle size can be determined by screening analysis. The particulate amorphous residue of SiO2 particulate in the event of passing through a mesh with a mesh width of 125 pm (120 mesh) preferably amounts up to no more than 10% by weight, particularly preferably no more than 5% by weight. weight and even more particularly preferably not more than 2% by weight.
    [0053] The screen residue is determined using the machine screening method described in DIN 66165 (part 2), in which a chain ring is additionally used as a screening aid.
    [0054] It has also proved advantageous if the particulate amorphous SiO2 residue used according to the invention through a single pass through a screen with a mesh size of 45 pm (325 mesh) amounts up to no more than about 10 % by weight, particularly preferably not more than about 5% by weight and even more particularly preferably not more than about 2% by weight (sorting according to DIN ISO 3310).
    [0055] By means of scanning electron microscopic images the ratio of primary particles (non-agglomerated, ungrown and non-fused particles) to secondary particles (agglomerated, intergrown and / or fused particles, including particles that (clearly) do not / 37 have a spherical shape), particulate amorphous S1O2 can be determined. These images were obtained using a scanning electron microscope Nova NanoSem 230 of ultra high resolution of FEI, equipped with a Lens Detector Through (TLD).
    [0056] For this purpose the samples were dispersed in distilled water and then applied to an aluminum retainer with a copper band that adheres before the water is evaporated. In this way details of the primary particle shape can be viewed up to 0.01 pm.
    [0057] The ratio of primary particles to secondary particles of particulate amorphous SiO2 advantageously characterized as in the sequence, independently of each other:
    a) More than 20% of the particles, preferably more than 40%, particularly preferably more than 60% and even more particularly preferably more than 80%, based on the total number of particles, are present in the form of primary particles essentially spherical, in each case especially with the limit values mentioned above in the form of spherical primary particles with diameters of less than 4 pm, and particularly preferably less than 2 pm.
    b) More than 20% by volume of the particles, preferably more than 40% by volume, particularly preferably more than 60% by volume and even more particularly preferably more than 80% by volume, based on a volume of the particles cumulative, they are present in the form of essentially spherical primary particles, in each case particularly with the above limit values in the form of spherical primary particles with diameters of less than 4 pm, and particularly preferably less than 2 pm. The calculation of the respective volumes of the individual particles and the cumulative volume of all the particles was carried out assuming spherical symmetry for each individual particle and using the diameters determined by the SEM image formation for the respective particles.
    c) More than 20% area, preferably more than 40% area, particularly preferably more than 60% area and even more particularly preferably more than 8% area, based on the cumulative surface area of the particles , are present in the form of essentially spherical primary particles, in each case especially with the limit values given above, in the form of spherical primary particles with diameters of less than 4 pm and particularly preferably less than 2 pm.
    [0058] The percentages were determined based on statistical evaluations of a plurality of SEM images, as shown in Fig. 1 and Fig. 2, in which agglomeration / intergrowth / coalescence should only be classified in this way if the respective contours of individual adjacent spherical (coalescent) primary particles are no longer recognizable. In the case of overlapping particles, in which the respective contours of the spherical geometries are recognizable (otherwise), classification as primary particles is made even if the view does not allow current classification because of the two-dimensionality of the photographs. In determining surface area, only the visible particle areas are evaluated and contribute to the total.
    [0059] Additionally the specific surface of the amorphous particulate SiO 2 used according to the invention was determined with the aid of gas adsorption measurements (BET method, nitrogen) according to DIN 66131. It was found that a correlation appears to exist between BET and compressibility. The suitable particulate amorphous SiO2 used in accordance with the invention has a BET of less than or equal to 35 m 2 / g, preferably less than or equal to 20 m2 / g, particularly preferably less than or equal to 17 m2 / g g and even more particularly preferably less than or equal to 15 m2 / g. The lower / 37 limits are greater than or equal to 1 m 2 / g, preferably greater than or equal to 2 m2 / g, particularly preferably equal to 3 m2 / g and even more particularly preferably preferably greater than or equal to 4 m2 / g.
    [0060] Depending on the intended application and the desired resistance level, between 0.1% by weight and 2% by weight of particulate amorphous SiÜ2 is used, preferably between 0.1% by weight and 1.8% by weight and particularly preferably between 0.1% by weight and 1.5% by weight, in each case based on the mold base material.
    [0061] The ratio of inorganic binder to particulate amorphous SiO 2 used according to the invention can be varied within wide limits. This offers the opportunity to vary the initial resistances of the taps a lot, that is, the resistance immediately after removal of the modeling tool, without having a substantial effect on the final resistance. This is of great interest especially in light of metal casting. On the one hand, high initial resistances are desired here in order to transport the males immediately after production without problems or combine them in whole male packages, and on the other hand the final resistances should not be so high as to avoid problems in the male break after casting.
    [0062] Based on the weight of the binder (including any diluents or solvents that may be present), particulate amorphous SiO 2 is preferably present in a fraction of 2% by weight to 60% by weight, particularly preferably 3% by weight at 55% by weight and even more particularly preferably from 4% by weight to 50% by weight. The amorphous SiO2 (particulate) produced in a synthetic way corresponds to the amorphous SiO2 particulate according to the terminology of the claims, among other things, and is especially used as a powder, in particular with a water content of less than 5% in weight, preferably less than 3% by weight, especially less than 2% by weight (water content determined by the Karl Fischer method). Regardless of this, ignition loss (at 400 ° C) preferably amounts up to less than 6, less than 5 or even less than 4% by weight.
    [0063] The addition of the amorphous particulate SiO2 used according to the invention can occur before or after or in a mixture together with the addition of the binder, directly to the refractory material. Preferably the particulate amorphous SiO2 used according to the invention is added to the refractory material in dry and powder form after the addition of binder.
    [0064] According to a further embodiment of the invention, first a premixture of SiO2 with an aqueous alkaline hydroxide, such as sodium hydroxide, and optionally the binder or part of the binder is produced, and this is then mixed into the material of refractory mold base. The binder or fraction of binder that may still be available, having not been used for the premix, can be added to the mold base material before or after the addition of the premix or together with it.
    [0065] According to an additional embodiment, in addition to particulate amorphous SiO2, a synthetic particulate amorphous SiO2 not according to the invention but according to EP 1802409 B1 can be used, for example, in a ratio of 1 less than that 1.
    [0066] Mixtures of SiO2 according to the invention and not according to the invention can be advantageous if the effect of particulate amorphous SiO2 is to be "attenuated." By adding amorphous S1O2 according to the invention and not according to the invention for mixing mold material, the resistances and / or the compacting capacities of castings molds can be adjusted in a systematic way.
    [0067] In an additional embodiment, in the case of an inorganic binder based on water-soluble glass, the mixture of mold material according to the invention may comprise a compound containing phosphorus. Such an additive is preferred in the case of very thin wall sections / 37 of a casting mold and especially in the case of taps, since in this way the thermal stability of the taps of the thin wall section of the casting part can be increased. This is especially significant if the liquid metal encounters an inclined surface after casting and has a strong erosive effect on it because of the high metallostatic pressure or can lead to deformations of especially thin wall sections of the casting mold.
    [0068] In this process, suitable phosphorus compounds have little or no effect on the processing time of the mold material mixtures according to the invention. An example of this is sodium hexametaphosphate. Additional suitable representatives and the amounts to be added are described in WO 2008/046653, and therefore this is also incorporated in the disclosure of the present patent.
    [0069] Although the mold material mixtures according to the invention already have improved flow capacity compared to the prior art, it can be further increased if desired by adding lamellar type lubricants, for example , to completely fill molding tools that have particularly narrow passages. According to an advantageous embodiment of the invention the mixture of mold material according to the invention contains a fraction of lamellar type lubricants, especially graphite or MoS2. The amount of lamellar type lubricant added, especially graphite, preferably amounts up to 0.05% by weight to 1% by weight based on the mold base material.
    [0070] Instead of the lamellar type lubricant, surface active substances, especially surfactants, can be used, and in the same way they will improve the flow capacity of the mold material mixture even more.
    [0071] Suitable representatives of such compounds are described, for example, in WO 2009/056320 (= US 2010/0326620 A1). In particular, surfactants with sulfuric acid or sulfonic acid groups can be mentioned here. Additional suitable representatives and the respective amounts for the addition are described in detail, and therefore this is also incorporated in the disclosure of the present patent.
    [0072] In addition to the mentioned components, the mixture of mold material according to the invention may comprise additional additives. For example, release agents can be added to facilitate the removal of the males from the modeling tool. Suitable release agents may include, for example, calcium stearate, fatty acid esters, waxes, natural resins or special alkyd resins. As long as these release agents are soluble in the binder and do not separate from it even after prolonged storage, especially at low temperatures, they may already be present in the binder component, but they can also be part of the additive or added to the mixture. mold material as a separate component.
    [0073] Organic additives can be added to improve the casting surface. Suitable organic additives, for example, are phenol - formaldehyde resins such as novolacs, epoxy resins such as bisphenol A - epoxy resin, bisphenol F - epoxy resin or epoxidized novolacs, polyols such as polyethylene or polypropylene glycols, glycerol or polyglycerol, such polyolefins such as polyethylene or polypropylene, olefin copolymers such as ethylene and / or propylene with additional comonomers such as vinyl acetate or styrene and / or diene monomers such as butadiene, polyamides such as polyamide-6, polyamide-12 or polyamide-6, 6, natural resins such as balsamic resin, fatty acid esters such as cetyl palmitate, fatty acid amides such as ethylene diamine bis-stearamide, metal soaps such as bivalent or trivalent metal stearates or oleatates, or carbohydrates, for example, dextrins . Carbohydrates, especially 37 dextrins, are especially suitable. Suitable carbohydrates are described in WO 2008/046651 A1. Organic additives can be used both as the pure material and in a mixture with various other organic and / or inorganic compounds.
    [0074] Organic additives are preferably added in an amount of 0.01% by weight to 1.5% by weight, particularly preferably 0.05% by weight to 1.3% by weight and even more particularly preferably 0.1 % by weight to 1% by weight, in each case based on the mold material.
    [0075] Additionally, silanes can also be added to the mold material mixture according to the invention to increase the resistance of the males to high atmospheric humidity and / or to water-based mold coatings. According to a further preferred embodiment the mixture of mold material according to the invention therefore contains a portion of at least one silane. Suitable silanes are, for example, aminosilanes, epoxysilanes, mercaptosilanes, hydroxysilanes and ureidosilanes. Examples of suitable silanes are γ-aminopropyl-trimethoxy silane, γ-hydroxypropyl-trimethoxy silane, 3-ureidopropyl-trimethoxy silane, γmercaptopropyl-trimethoxy silane, γ-glycidoxypropyl-trimethoxy silane, β- (3,4epoxycyclohexyl) -trimethoxy silane ^ - (aminoethyl) - γ-aminopropyl-trimethoxy silane and the trietoxy analog compounds thereof. The silanes mentioned, especially the amino silanes, can also be prehydrated. Typically about 0.1% by weight to 2% by weight, based on the binder, preferably 0.1% by weight to 1% by weight are used.
    [0076] Additional suitable additives are alkali metal siliconates, for example, potassium methyl siliconate, wherein about 0.5% by weight to about 15% by weight, preferably about 1% by weight to about 10% by weight and particularly preferably about 1% by weight to about 5% by weight, based on the binder can be used.
    / 37 [0077] If the mold material mixture comprises an organic additive, it can basically be added to the mixture at any time in the production process of the mixture. The addition can occur in bulk or in the form of a solution.
    [0078] Organic water-soluble additives can be used in the form of an aqueous solution. If organic additives are soluble in the binder and can be stored in a stable manner without decomposition for several months, they can also be dissolved in the binder and thus added to the mold material together with them. Water-insoluble additives can be used in the form of a dispersion or a paste. The dispersions or pastes preferably contain water as the liquid medium.
    [0079] If the mold material mixture contains alkaline silanes and / or methyl siliconates, in general they are additional by incorporating them into the binder in advance. However, they can also be added to the mold material as separate components.
    [0080] Inorganic additives can also have a positive effect on the properties of the mold material mixtures according to the invention. For example, the carbonates mentioned in AFS Transactions, vol. 88, pp. 601 - 608 (1980) and / or vol. 89, pp. 47 - 54 (1981) increase the resistance to moisture in males during storage, while the phosphorus compounds known from WO 2008/046653 (= CA 2666760 A1) increase the thermal resistance of males when binders based on soluble glass in water are used.
    [0081] Alkaline borates as constituents of water-soluble glass binders are disclosed, for example, in EP 0111398.
    [0082] Suitable inorganic additives, based on BaSO4, to enhance the casting surface are described in DE 102012104934.3 and can be added to the mold material mixture as a / 37 substitute for part or all of the aforementioned organic additives .
    [0083] Additional details such as the respective quantities for the addition are described in detail in DE 102012104934.3, and therefore this is also incorporated in the disclosure of the present patent.
    [0084] Despite the high strengths that can be achieved with the mold material mixture according to the invention, the cores produced from these mold material mixes have good disintegration after casting, especially in aluminum casting. The use of taps produced from the mold material mixtures according to the invention, however, is not exclusively limited to light metal casting. Castings molds are generally suitable for metal casting. Such metals also include, for example, non-ferrous metals such as brass or bronzes and ferrous metals.
    [0085] The figures show:
    [0086] Fig. 1 is a scanning electron microscopic image of particulate amorphous SiO2 used according to the invention;
    [0087] Fig. 2 is a scanning electron microscopic photograph of amorphous SiO2 not according to the invention produced during the manufacture of silicon / silicon iron;
    [0088] Fig. 3 is a test piece in the form of an inlet port male.
    [0089] The invention will be explained in more detail based on the examples that follow, without being limited to these.
    Examples:
    1. Hot curing
    1.1. Experiment 1: core strengths and weights as a function of the added particulate amorphous SiO2 type
    1.1.1 Preparation of mold mixtures / 37
    Without addition of S1O2 [0090] Quartz sand was placed in the basin of a Hobart mixer (model HSM 10). While stirring, the binder is then added and in each case intensively mixed with the sand for 1 minute. The sand used, the type of binder and the respective amounts added are shown in Table 1.
    1.1.1.2 with addition of SiO2 [0091] The procedure of 1.1.1.1 was followed, except that after adding the binder to the mixture of mold material, particulate amorphous SiO2 was added and it was also mixed for 1 minute. The type of particulate amorphous SiO2 and the amounts added are shown in Table 1.
    Table 1 (Experiment 1) Composition of mixtures of mold material
    H32 quartz sand [PBW] Binder [PBW] Amorphous S1O2 [PBW] ZrO2 separate [PBW] added between1.1 100 2.0 a) not according to invention 1.2 100 2.0 a) 0.5 d) 0.025 n) not according to invention 1.3 100 2.0 a) 0.5 e) 0.025 o) not according to invention 1.4 100 2.0 a) 0.475 e)not according to invention 1.5 100 2.0 a) 0.475 e)not according to invention 1.6 100 2.0 a) 0.5 f)according to invention 1.7 100 2.0 a) 0.5 g)according to invention 1.8 100 2.0 a) 0.5 h)according to invention 1.9 100 2.0 a) 0.5 i)according to invention 1.10 100 2.0 b) 0.5 e)not according to invention 1.11 100 2.0 b) 0.5 f)not according to invention 1.12 100 2.0 b) 0.5 e)according to invention 1.13 100 2.0 c) 0.5 f)not according to invention 1.14 100 2.0 c) not according to invention 1.15 100 2.0 c) according to invention
    PBW = parts by weight
    a) alkaline water-soluble glass; molar modulus of approximately 2.1; solids content of approximately 35% by weight
    b) Sodium polyphosphate solution; 52% by weight (NaPO3) n with n = approximately 25; 48% water by weight
    c) Mixture of 83% by weight of a) and 17% by weight of b)
    d) Microsilica 971 U (Elkem AS; manufacturing process: silicon / ferrosilicon production) / 37
    e) Microsilica white GHL DL 971 W (RW Silicium GmbH; manufacturing process: see d)
    f) Microsilica POS B-W 90 LD (Possehl Erzkontor GmbH; manufacturing process: production of ZrO2 and SiO2 from ZrSiO4)
    g) Silica smoke (Doral Fused Materials Pty., Ltd .; manufacturing process: see f)
    h) SiF-B white silica smoke (Cofermin Rohstoffe GmbH & Co. KG; manufacturing process: see f)
    i) 605 MID silica smoke (TAM Ceramics LLC; manufacturing process: production of ZrO2 stabilized by Ca and SiO2 from ZrSiO4)
    n) 45 pm molten monoclinic zirconia (Cofermin Rohstoffe GmbH & Co. KG)
    o) 45 pm limestone stabilized molten zirconia (Cofermin Rohstoffe GmbH & Co. KG)
    1.1.1.2. with addition of SiO2
    1.1.2 Production of test pieces [0092] To test mixtures of mold material, rectangular test bars measuring 150 mm x 22.36 mm x 22.36 mm were prepared (so-called Georg Fischer bars) . A portion of a mixture of mold material was transferred to the storage compartment of a H 2.5 Hot Box male firing machine from Rõperwerk-GieBereimaschinen GmbH, Viersen, DE, the shaping tool from which it is heated to 180 ° Ç. The rest of the respective mixture of mold material was carefully stored in a closed container to protect it from drying out and avoid premature reaction with the CO2 present in the air until it was time to refill the tapping machine.
    [0093] The mold materials were introduced using compressed air (5 bar / 0.5 mPa) from the storage compartment / 37 for the modeling tool. The residence time in the hot molding tool to cure mixtures is 35 seconds. To speed up the curing process, hot air (2 bar / 0.2 mPa, 100 ° C through the tool inlet) was passed through the shaping tool during the last 20 seconds. The modeling tool was opened and the test bar was removed. The test pieces for determining the male weights were made using this method.
    1.1.3. Testing of test pieces
    1.1.3.1 Resistance test [0094] To determine the bending strengths, the test bars were placed in a Georg Fischer resistance tester equipped with a 3-point bending device and the force required to break the test bar was measured .
    [0095] The bending strengths were determined according to the following scheme:
    seconds after removal (hot resistance) Approximately 1 hour after removal (cold resistance) [0096] The results are shown in Table 2.
    1.1.3.2 Determination of the male weight [0097] Before determining the cold resistances, the Georg Fischer bars were weighed on a precise laboratory scale up to 0.1 g. The results are shown in Table 2.
    Table 2 (Experiment 1) Resistance to bending and male weights
    # Resistance to hot [N / cm 2 ] Cold resistances: [N / cm 2 ] Male weight[g] 1.1 90 380 123.2not according to invention 1.2 150 480 123.1not according to invention 1.3 155 500 123.6not according to invention 1.4 150 485 123.7not according to invention 1.5 150 485 123.5not according to invention 1.6 180 575 127.2according to invention 1.7 185 600 127.1according to invention 1.8 180 580 128.2according to invention 1.9 155 530 126.2according to invention 1.10 10 145 119.7not according to invention
    / 37
    1.11 45 160 121.7not according to invention 1.12 50 175 125.9according to invention 1.13 95 405 122.7not according to invention 1.14 145 500 121.1not according to invention 1.15 160 550 125.3according to invention
    PBW = parts by weight
    Results:
    [0098] It is apparent from Table 2 that the production methods of particulate amorphous SiO2 manufactured in a synthetic way have a distinct effect on the characteristics of the males. Males produced with an inorganic binder and SiO2 according to the invention have higher strengths and higher male weights than males containing SiO2 not according to the invention.
    [0099] Examples 1.5 and 1.6 show that the positive effects are not based on the presence of ZrO2 in the amorphous SiO2 according to the invention, originating from the ZrSiO4 process.
    1.2. Experiment 2: Flow capacity of mixtures of mold material as a function of the type of particulate amorphous SiO2 produced in a synthetic way, sand and firing pressure.
    1.2.1. Production of mixtures of mold material [00100] Mixtures of mold material were produced in analogy to 1.1.1. Their compositions are shown in Table 3.
    Table 3 (Experiment 2) Resistance to bending and male weights
    # Mold base material [PBW] Cold resistances: [N / cm 2 ] Male weight[g] in Surfactant2.1 100 a) 2.0 d) 0.5 f)not according to 2.2 100 a) 2.0 e) 0.5 g) 0.04 i) invention 2.3 100 a) 2.0 d) 0.5 h) 0.04 i) not according to 2.4 100 b) 2.0 d) 0.5 f)invention 2.5 100 b) 2.0 d) 0.5 h)according to invention 2.6 100 c) 2.0 d) 0.5 f)not according to 2.7 100 c) 2.0 d) 0.5 h)invention 2.8 100 a) 2.0 d) 0.5 f)according to invention 2.9 100 a) 2.0 d) 0.5 h)not according to inventionaccording to invention not according to inventionaccording to invention
    PBW = parts by weight / 37
    a) H 32 Haltern quartz sand (Quarzwerke Frechen)
    b) water-soluble glass F32 Frechen (Quarzwerke Frechen)
    c) Quartz sand Sajdikove Humenece SH 21 (Quarzwerke Frechen)
    d) alkaline water-soluble glass; molar modulus of approximately 2.1; solids content of approximately 40% by weight
    e) 1.8 PBW of alkaline water-soluble glass d) + 0.2 PBW of NaOH (33% by weight) corresponding to EP 2014392
    f) Microsilica white GHL DL 971 W (RW Silicium GmbH; manufacturing process: silicon / ferrosilicon production
    g) Suspension of 25% nano SiO2, 25% micro SiO2 and 50% water corresponding to EP 2014392
    h) Microsilica POS 90 LD (Possehl Erzkontor GmbH; manufacturing process: production of ZrO2 and SiO2 from ZrSiO4.
    i) Texapon EHS (Cognis)
    1.2.2 Production of test pieces [00101] To investigate the effect of particulate amorphous SiO2 produced in a synthetic way on the flow capacity of mold material mixtures in additional detail, males from the casting practice, so-called Inlet port, were produced, which are larger and have more complex geometry than Georg Fischer bars (Fig. 3).
    [00102] Preliminary results also showed that the predicted value of this experiment is greater when a practical male of complex structure is used as a test piece when the Georg Fischer flowability test, with its simple geometry, is used (S. Hasse, GieBerei-Lexikon [Foundry Dictionary], Fachverlag Schiele und Schon). Three different sands with different particle shapes were used as / 37 base mold materials.
    [00103] Mold material mixtures were transferred to the storage compartment of an L 6.5 male firing machine, Roperwerk - GieBereimaschinen GmbH, GmbH, Viersen, DE, the shaping tool which was heated up to 180 ° C, and from there it was introduced to the modeling tool using compressed air. The pressures used in this process are shown in Table 4.
    [00104] The residence time in the hot tool to cure the mixtures was 35 seconds. To speed up the curing process, hot air (2 bar / 0.2 mPa, 150 ° C at the entrance to the tool) was passed through the modeling tool for the last 20 seconds.
    [00105] The modeling tool was opened and the test bars were removed.
    1.2.3. Determination of the male weights [00106] After refrigeration, the males were weighed on an accurate laboratory scale up to 0.1 g. The results are shown in Table 4.
    Table 4 (Experiment 2) Male weights from various mixes of mold material
    # Male weight [g]5 bar (0.5 mPa) 3 bar (0.3 mPa) 2 bar (0.2 mPa) 2.1 1297.7 1280.7 1238.0 not according to invention 2.2 1290.1 1270.4 1225.7 not according to invention 2.3 1357.0 1350.7 1314.0 according to invention 2.4 1244.3 1232.3 1205.0 not according to invention 2.5 1295.3 1274.0 1248.3 according to invention 2.6 1354.8 1335.9 1290.0 not according to invention 2.7 1393.7 1388.5 1356.0 according to invention 2.8 1323.0 1319.3 1298.0 not according to invention 2.9 1373.7 1367.7 1335.3 according to invention
    Result:
    [00107] Table 4 confirms, based on a male from the casting practice, the improved flowability of the mold materials according to the invention compared to the prior art. The positive effect is independent of the type of sand and the trigger pressure.
    / 37 [00108] The addition of a surfactant for SiO 2 according to the results of the invention in an additional improvement, although not as pronounced, the improvement of the flow capacity as when amorphous SiO 2 from other manufacturing processes it is used.
    2. Gas cure on unheated tools.
    2.1. Experiment 3: Core strengths and weights depending on the type of particulate amorphous SiO2 added.
    2.1.1. Preparation of mixtures of mold material [00109] Mixtures of mold material were prepared in analogy to 1.1.1. Their compositions are shown in Table 5.
    Table 5 (Experiment 3) Composition of mixtures of mold material
    # Quartz sand H 32 a) [PBW] Linker b) [PBW] Amorphous S1O2 [PBW] ZrO2 addedseparately [PBW]3.1 100 2.0 not according to invention 3.2 100 2.0 0.5 c) 0.025 g) not according to invention 3.3 100 2.0 0.475 c) 0.025 h) not according to invention 3.4 100 2.0 0.475 d) not according to invention 3.5 100 2.0 0.5 and according to invention 3.6 100 2.0 0.5 f) according to invention 3.7 100 2.0 0.5 h) according to invention
    PBW = parts by weight
    a) Quarzwerke Frechen GmbH
    b) alkaline water-soluble glass; molar modulus of approximately 2.33; solids content of approximately 40% by weight
    c) Microsilica 971 U (Elkem AS; manufacturing process: silicon / ferrosilicon production)
    d) Microsilica POS B-W 90 LD (Possehl Erzkontor GmbH; manufacturing process: production of ZrO2 and SiO2 from ZrSiO4)
    e) Silica smoke (Doral Fused Materials Pty., Ltd .; manufacturing process: see d)
    f) Silica smoke 605 MID (TAM Ceramics LLC; manufacturing process: production of ZrO2 stabilized by Ca and SiO2 from ZrSiO4) / 37
    g) 45 pm cast monoclinic zirconia (Cofermin Rohstoffe GmbH & Co. KG)
    h) Fused zirconia stabilized by 45 pm limestone (Cofermin Rohstoffe GmbH & Co. KG)
    2.1.2 Preparation of test pieces [00110] A portion of the mold material mixture produced according to 2.1.1 was transferred to the storage chamber of an H1 tapping machine from Roperwerk - GieBereimaschinen GmbH, GmbH, Viersen , IN. The rest of the mold material mixture was carefully stored in a closed container to protect it from drying out and avoid premature reaction with the CO2 present in the air until it was time to refill the tapping machine.
    [00111] The mold materials were fired using compressed air (4 bar / 0.4 mPa) for an unheated molding tool with two grooves for round cores with a diameter of 50 mm and a height of 40 mm.
    2.1.2.1. Cure with a combination of and air [00112] To cure, CO2 was first passed through the modeling tool, filled with the mold material mixture, for 6 seconds at a CO2 flow rate of 2 L / min and then compressed air at a pressure of 4 bar (0.4 mPa) was passed through the modeling tool filled with the mold material mixture. The temperatures of the two gases were about 23 ° C through entry into the modeling tool.
    2.1.2.2 Cure with CO2 [00113] To cure, CO2 at a flow rate of 4 L / min was passed through the modeling tool, filled with the mixture of mold material. The CO2 temperature was about 23 ° C through the entry into the modeling tool.
    [00114] CO2 gasification times are shown in Table / 37
    7.
    Table 6 (Experiment 3) Compressive strengths and core weights after curing with a combination of CO2 and air
    # Immediate resistances) [N / cm 2 ] Resistances after 24 h [N / cm 2 ] Male weight[g]]3.1 56 238 141.1 not according to invention 3.2 173 289 143.3 not according to invention 3.3 193 280 143.1 not according to invention 3.4 189 300 143.4 not according to invention 3.5 214 383 151.1 according to invention 3.6 197 371 149.3 according to invention 3.7 195 333 148.4 according to invention
    Table 7 (Experiment 3) Compressive strengths after storage at elevated temperature and atmospheric humidity, curing with a combination of CO2 and air
    # Immediate resistances ) [N / cm 2 ] Resistances after 24 h [N / cm 2 ] Resistances after 4 days [N / cm 2 ] Resistances after 6 days [N / cm 2 ]3.1 63 248 215 188 not according to 3.2 166 298 256 221 invention 3.5 205 396 384 373 not according to inventionaccording to invention
    a) Storage at 23 ° C / 50% relative humidity
    b) Storage for 24 h at 23 ° C / 50% relative humidity, then at 30 ° C / 80% relative humidity
    2.1.2.3. Air curing [00115] To cure, air at a pressure of 2 bar (0.2 mPa) was passed through the modeling tool, filled with the mixture of mold material. The air temperature was between about 22 and about 25 ° C through entry into the modeling tool.
    [00116] The gasification times with air are shown in Table 8.
    Table 8 (Experiment 3) Compressive strengths
    # Gasification time [seconds] Immediate resistances) [N / cm 2 ] Resistances after 24 h [N / cm 2 ] 10 12 643.1 15 20 57 not according to invention20 24 51 30 35 44 45 40 46 60 42 45
    / 37
    # Gasification time [seconds] Immediate resistances) [N / cm 2 ] Resistances after 24 h [N / cm 2 ] 90 43 38 10 33 673.2 15 42 65 not according to invention20 46 66 30 49 57 45 51 54 60 56 52 90 57 48 10 40 933.5 15 48 94 according to invention20 48 95 30 54 88 45 60 83 60 63 78 90 67 67
    2.1.3 Testing the test pieces [00117] After curing, the test pieces were removed from the modeling tool and their compressive strengths were determined with a Universal Zwick Testing Machine (Model Z 010) immediately, that is, a maximum of 15 seconds after removal. In addition, the compressive strengths of the test pieces were tested after 24 hours, and in some cases also after 3 and 6 days of storage in a conditioning chamber. Constant storage conditions were able to be guaranteed with a conditioning chamber (Rubarth Apparatus GmbH).
    [00118] Unless stated otherwise, a temperature of 23 ° C and a relative humidity of 50% have been defined. The values shown in the tables are average values from 8 males in each case. In order to check the compaction of the mold material mixtures during the production of the core, in the case of combined curing with CO2 and air the core weights were determined 24 hours after removal of the core boxes. Weighing was carried out on an accurate laboratory scale up to 0.1 g.
    [00119] The results of the resistance tests and the male weights, up to the degree that the last ones were performed, are shown in Tables 6 and 7 (cure with CO2 and air), Table 8 (cure with CO2), and Table 9 (air curing).
    / 37
    Table 9 (Experiment 3) Compressive strengths in the case of air curing
    # Gasification time [seconds] Immediate resistances) [N / cm 2 ] Resistances after 24 h [N / cm 2 ] 30 27 753.1 45 71 93 not according to invention60 101 104 30 41 1433.2 45 88 222 not according to invention60 123 273 30 32 2823.5 45 106 307 according to invention60 131 335
    Result:
    [00120] It is apparent from Tables 6 to 9 that the positive characteristics of particulate amorphous SiO2 compared to the prior art are not limited to hot curing (Table 2), but are also observed during curing of mold material mixtures using a combination of CO2 and air, using CO 2 , and using air.
    3. Cold curing
    3.1. Experiment 4: Core strengths and weights depending on the type of particulate amorphous SiO2 added
    3.1.1. Production of mixtures of mold material
    3.1.1.1. Without addition of SiO 2 [00121] Quartz sand from Quarzwerke Frechen GmbH was filled into the bowl of a Hobart mixer (model HSM 10). Then while stirring, first the curing agent and then the binder were added, and in each case the mixture was intensively stirred with sand for 1 minute.
    [00122] The respective quantities added as well as the type of curing agent and binder are presented in the individual experiments.
    3.1.1.2. With addition of SiO 2 [00123] The procedure as in 3.1.1 was followed, with the difference that after adding the binder to the mixture of mold material, the particulate amorphous SiO2 was also added and it was mixed in the same / 37 form for 1 minute. The amount added and the type of particulate amorphous SiO 2 are presented for the individual experiments.
    3.1.2 Preparation of test pieces [00124] The compositions of the mold material mixtures used to prepare the test pieces are shown in parts by weight (PBW) in Table 10.
    [00125] To test mixtures of mold material, rectangular test bars with dimensions of 220 mm x 22.36 mm x 22.36 mm were produced (so-called Georg Fischer bars).
    [00126] Part of a mixture prepared according to 3.1.1 was introduced manually in a modeling tool with 8 grooves, was introduced manually in a modeling tool and compressed by pressing with a hand plate.
    [00127] The processing time, that is, the time in which a mixture of mold material can be compacted without difficulty, was determined visually. The fact that the processing time has been exceeded can be recognized when a mixture of mold material flows more freely, but rolls like a groove slice. The processing times for the individual mixtures are shown in Table 10.
    [00128] To determine the extraction time ((ST), that is, the time after which a mixture of mold material has solidified to the point where it can be removed from the modeling tool, a second part of the respective mixture was packed by hand into a round mold 100 mm high and 100 mm in diameter, and similarly compressed with a hand plate. So the surface hardness of the compressed mold material mixture was tested at certain intervals with the Georg Fischer's surface hardness tester As soon as a mixture of mold material is so difficult that the test ball no longer penetrates the core surfaces, the extraction time has been reached The extraction times of the individual mixtures are shown in Table 10.
    Table 10 (Experiment 4) Composition of mixtures of mold material
    Quartz sand H 32 a) [PBW] Linker b) [PBW] Catalyst [PBW] Amorphous SiO2 [PBW]4.1 100 2.5 0.35 c) not according to invention 4.2 100 3.0 0.35 c) 0.5 e) not according to invention 4.3 100 2.5 0.35 c) 0.5 f) not according to invention 4.4 100 2.5 0.35 c) 0.5 g) according to invention 4.5 100 2.5 0.35 c) 0.5 h according to invention 4.6 100 2.5 0.35 c) 0.5 e) according to invention 4.7 100 2.5 0.35 d) 0.5 f) not according to invention 4.8 100 2.5 0.35 d) 0.5 g) not according to invention 4.9 100 2.5 0.35 d) not according to invention 4.10 100 2.5 0.35 d) according to invention 4.11 100 2.5 0.35 d) according to invention
    PBW = parts by weight
    a) Quarzwerke Frechen GmbH
    b) Nuclesil 50 (Cognis)
    c) Catalyst 5090 (ASK Chemicals GmbH), ester mixture
    d) Lithopix P26 (Zschimmer & Schwarz
    e) Microsilica 971 U (Elkem SA; manufacturing process: silicon / ferrosilicon production)
    f) Microsilica POS BW 90 LD (Possehl Erzkontor GmbH; manufacturing process: production of ZrO 2 and SiO 2 from ZrSiO 4 )
    g) Silica smoke (Doral Fused Materials Pty., Ltd .; manufacturing process: see f)
    h) Silica smoke 605 MID (TAM Ceramics LLC; manufacturing process: production of ZrO 2 stabilized by Ca and SiO 2 from ZrSiO 4 )
    3.1.3 Testing the test pieces
    3.1.3.1. Resistance test [00129] To determine the bending strengths, the test bars were positioned on a Georg Fischer Resistance Test Machine equipped with a 3-point bending device and the force that leads to the breaking of the test bars was measure.
    [00130] The bending resistances were determined according to the following schemes:
    / 37 hours after male production hours after male production [00131] The results are shown in Table 10.
    3.1.3.2. Determination of the male weight [00132] Before the resistances were determined, Georg Fischer's bars were weighed on an accurate laboratory scale up to 0.1 g. The results are shown in Table 10.
    Results:
    [00133] Table 11 shows the positive effects of adding particulate amorphous SiO2 in terms of strength and male weight in cold curing with an ester mixture (Examples 4.1 to 4.6) and a phosphate curing agent (Examples 4.7 to 4.11) compared to the prior art.
    Table 11 (Experiment 4) Bending strengths and core weights
    PT a) / ST b) [min] Resistances after 4 h [N / cm 2 ] Resistances after 4 h [N / cm 2 ] Weight ofmale[g]4.1 15/80 145 250 119.5 not according to 4.2 17/85 125 265 117.0 invention 4.3 4/75 185 290 119.7 not according to 4.4 3/70 215 425 125.5 invention 4.5 5/70 250 475 124.9 not according to 4.6 7/80 210 385 123.8 invention 4.7 3/80 175 270 115.8 according 4.8 4/85 160 290 115.0 invention 4.9 3/65 195 335 116.0 according 4.10 4/60 210 415 121.3 invention 4.11 4/60 215 415 120.1 accordinginventionnot according to inventionnot according to inventionnot according to inventionaccordinginventionaccordinginvention
    / 5
    权利要求:
    Claims (20)
    [1]
    1. Mixing of mold material to produce taps and molding forms for metal processing, characterized by the fact that it comprises at least:
    • a base material of refractory mold;
    • an inorganic binder; and • Amorphous particulate SiO2 obtained by thermal decomposition from ZrSiO4 to ZrO2 and SiO2, such that the amorphous particulate SiO2 comprises zirconium compounds, calculated as ZrO2, in an amount greater than 0.01% by weight and less than 12% in Weight.
    [2]
    2. Mold material mixture according to claim 1, characterized by the fact that the amorphous particulate SiO2 has a BET of more than or equal to 1 m 2 / g and less than or equal to 35 m 2 / g, preferably less than or equal to 17 m2 / g and particularly less than or equal to 15 m2 / g.
    [3]
    Mixture of mold material according to any one of the preceding claims, characterized in that the average particle size (diameter) determined by the dynamic light scattering of the amorphous particulate SiO2 in the mold material mixture is between 0.05 pm and 10 pm, especially between 0.1 pm and 5 pm, and particularly preferably between 0.1 pm and 2 pm.
    [4]
    Mixture of mold material according to any one of the preceding claims, characterized in that the mixture of mold material contains particulate amorphous SiO2 in quantities of 0.1 to 2% by weight, preferably 0.1 to 1 , 5% by weight, in each case based on the mold base material and independently of this, 2 to 60% by weight, particularly preferably 4 to 50% by weight, based on the weight of the binder, where the solids fraction binder amounts of 25 to 65% by weight, preferably 30 to 60% by weight.
    Petition 870190062714, of 07/04/2019, p. 12/16
    2/5
    [5]
    Mixture of mold material according to any one of the preceding claims, characterized in that the particulate amorphous SiO2 has a water content of less than 10% by weight, especially less than 5% by weight and particularly preferably less than 2% by weight and independently it is used especially as a powder.
    [6]
    Mixture of mold material according to any one of the preceding claims, characterized in that the mixture of mold material contains a maximum of 1% by weight, preferably a maximum of 0.2% by weight of organic compounds.
    [7]
    7. Mixing of mold material according to at least one of the preceding claims, characterized in that the inorganic binder is at least a water-soluble phosphate glass, a water-soluble borate and / or water-soluble glass and especially a water-soluble glass with a molar module of SiO2 / M2O in the range 1.6 to 4.0, especially 2.0 less than 3.5, where M represents lithium, sodium and / or potassium.
    [8]
    Mixture of mold material according to at least one of the preceding claims, characterized in that the mixture of mold material contains 0.5 to 5% by weight water-soluble glass, preferably 1 to 3.5% by weight weight water-soluble glass, based on the mold base material, wherein the solids fraction of the amounts of water-soluble glass is from 25 to 65% by weight, preferably from 30 to 60% by weight.
    [9]
    Mixture of mold material according to at least one of the preceding claims, characterized in that the mixture of mold material additionally contains surfactants, preferably selected from one or more members of the group of anionic surfactants, especially those with a sulfonic acid or sulfonate group,
    Petition 870190062714, of 07/04/2019, p. 13/16
    3/5 or especially comprising oleyl sulphate, myristyl sulphate, lauryl sulphate, decyl sulphate, octyl sulphate, 2-ethylhexyl sulphate, 2-ethyloctyl sulphate, 2-ethylldecyl sulphate, palmitoleyl sulphate, linolyl sulphonate, hexyl phosphate, 2-ethyl -hexyl phosphate, capryl phosphate, lauryl phosphate, myristyl phosphate, palmityl phosphate, palmitoleyl phosphate, oleyl phosphate, stearyl phosphate, poly- (1,2-ethanediyl) phenol-hydroxy phosphate, poly- (1,2-ethanediyl) stearyl phosphate, and poly- (1,2-ethanediyl) -oleyl phosphate.
    [10]
    Mixture of mold material according to claim 9, characterized in that the surfactant is present in the mixture of mold material in a fraction of 0.001 to 1% by weight, particularly preferably 0.01 to 0.2% by weight, based on the weight of the refractory mold base material.
    [11]
    Mixture of mold material according to at least one of the preceding claims, characterized in that the mixture of mold material also contains graphite, preferably from 0.05 to 1% by weight, especially 0.05 to 0, 5% by weight, based on the weight of the refractory mold base material.
    [12]
    Mixture of mold material according to at least one of the preceding claims, characterized in that the mixture of mold material also contains at least one compound containing phosphorus, preferably 0.05 and 1.0% by weight , especially preferably 0.1 and 0.5% by weight, based on the weight of the refractory mold base material.
    [13]
    13. Mixing of mold material according to at least one of the preceding claims, characterized by the fact that amorphous particulate SiO2 is used as a powder, preferably anhydrous, optionally in addition to any mixture caused by ambient air.
    [14]
    14. Mixing of mold material according to at least one of the preceding claims, characterized by the fact that a curing agent is added to the mixture of mold material, especially by
    Petition 870190062714, of 07/04/2019, p. 14/16
    4/5 minus an ester or phosphate compound.
    [15]
    15. Method for producing cores or casting molds characterized by the fact that it comprises:
    • preparing the mold material mixture as defined in at least one of claims 1 to 14, • positioning the mold material mixture in a mold, and • curing the mold material mixture.
    [16]
    16. Method according to claim 15, characterized in that the mixture of mold material is introduced into the mold with compressed air using a tapping machine and the mold is a modeling tool and the modeling tool has a or more gases that flow through it, especially CO2.
    [17]
    17. Method according to claim 15 or 16, characterized in that the mold material mixture is exposed to a temperature of at least 100 ° C for less than 5 min to cure it.
    [18]
    18. Method according to at least one of claims 15 to 17, characterized in that the mixture of hot-cured mold material, especially at 180 ° C, in the form of a 220 mm x Georg Fischer test bar 22.36 mm 22.36 mm, which using particulate amorphous SiO 2 has a male weight increased by 1%, preferably 1.5%, especially preferably 2.0%, particularly preferably 2.5% and even more particularly preferably 3.0%, with respect to a Georg Fischer test bar, similarly 220 mm x 22.36 mm 22.36 mm, produced under the same conditions and with the same mixture of mold material, but using Microsilica Elkem 971 instead of particulate amorphous SiO2 as defined in one of claims 1 to 13.
    [19]
    19. Mold or core, characterized by the fact that it can be obtained according to the method as defined in any of the
    Petition 870190062714, of 07/04/2019, p. 15/16
    5/5 claims 15 to 18.
    [20]
    20. Use of a mixture of mold material as defined in any of claims 1 to 14, characterized in that it is for melting aluminum, preferably also containing hollow microspheres, especially aluminum silicate hollow microspheres and / or hollow borosilicate microspheres.
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    公开号 | 公开日
    KR102104999B1|2020-06-01|
    EP3950168A1|2022-02-09|
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    JP6397415B2|2018-09-26|
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    KR20150074109A|2015-07-01|
    RU2015118399A|2016-12-10|
    WO2014059967A2|2014-04-24|
    DE102012020509A1|2014-06-12|
    EP2908968A2|2015-08-26|
    EP2908968B1|2021-11-24|
    BR112015008549A2|2017-07-04|
    US10092946B2|2018-10-09|
    RU2650219C2|2018-04-11|
    CN104736270B|2018-10-09|
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    法律状态:
    2018-11-21| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-04-09| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2019-10-08| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2019-11-19| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 18/10/2013, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 18/10/2013, OBSERVADAS AS CONDICOES LEGAIS |
    优先权:
    申请号 | 申请日 | 专利标题
    DE102012020509.0A|DE102012020509A1|2012-10-19|2012-10-19|Forming substance mixtures based on inorganic binders and process for producing molds and cores for metal casting|
    PCT/DE2013/000610|WO2014059967A2|2012-10-19|2013-10-18|Mould material mixtures on the basis of inorganic binders, and method for producing moulds and cores for metal casting|
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