Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22C—FOUNDRY MOULDING
  • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
  • B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
  • B22C1/18—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of inorganic agents
  • B22C1/186—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of inorganic agents contaming ammonium or metal silicates, silica sols
  • B22C1/188—Alkali metal silicates
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22C—FOUNDRY MOULDING
  • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
  • B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
  • B22C1/18—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of inorganic agents
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22C—FOUNDRY MOULDING
  • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
  • B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
  • B22C1/18—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of inorganic agents
  • B22C1/186—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of inorganic agents contaming ammonium or metal silicates, silica sols

Definitions

• the present invention relates to a process for preparing a molding material mixture or for producing a molding material mixture and a molded article thereof, preferably a mold or a core, for use in the foundry industry, wherein the molding material mixture comprises a mold base material and a solution or dispersion comprising lithium-containing water glass, with the steps (1) producing or providing a kit at least comprising as separate components: (K1) an aqueous solution or dispersion comprising water glass and (K2a) a first water-glass-free solution or dispersion comprising lithium ions dissolved in water and preferably (K2b) one second water-glass-free solution or dispersion, preferably comprising lithium ions dissolved in water in a lower concentration than in component (K2a), and then (2) producing a mixture of the molding base with a proportion of component (K1) and with a proportion of component (K2 a) and optionally with a proportion of component (K2b).
• the present invention relates to an aforementioned kit, in particular for use in the method according to the invention.
• the present invention also relates to a plant for producing an intermediate solution or dispersion comprising lithium-containing waterglass, for use in the production of a molding material mixture or for producing a molding material mixture and a molding thereof.
• Casting molds are essentially composed of molds and molds and cores which, after assembly, constitute the negative molds of the casting to be produced.
• These cores and molds are molded articles and are usually made of a refractory molding base material, for example quartz sand, and a suitable binder system, which gives the mold sufficient mechanical strength after removal from the mold.
• the refractory molding base material is preferably particulate and in a free-flowing form, so that it can be filled (after incorporation into a molding material mixture) in a suitable mold and compacted there.
• the binder produces a firm cohesion between the particles of the molding base material, so that the casting mold obtains the required mechanical stability.
• Molds and the moldings contained therein must meet various requirements. In the casting process itself, they must first have sufficient strength and temperature resistance in order to be able to absorb the liquid metal in the cavity formed from one or more casting molds. After the start of the solidification process, the mechanical stability of the casting is then ensured by a solidified metal layer which forms along the walls of the casting mold.
• the material of the casting mold should then decompose under the influence of the heat given off by the metal in such a way that it loses its mechanical strength, thus eliminating the cohesion between individual particles of the refractory material.
• the casting mold decays again into fine particles of the molding base material, which can be easily removed from the casting.
• both organic and inorganic binders can be used, the curing of which can be effected in each case by cold or hot processes.
• Cold processes are those processes which are carried out essentially without heating the mold used for core production, generally at room temperature or at a temperature caused by a possible reaction. Curing takes place, for example, by passing a gas through the molding material mixture to be cured, thereby triggering a chemical reaction.
• hot processes the molding material mixture is heated to a sufficiently high temperature after molding, for example by the heated mold, to expel the solvent contained in the binder and / or to initiate a chemical reaction by which the binder is cured.
• organic binders based on phenolic resin have the disadvantage that they decompose during casting and in some cases emit considerable amounts of pollutants such as, for example, benzene, toluene and xylene.
• pollutants such as, for example, benzene, toluene and xylene.
• the casting of organic binders usually leads to undesirable odor and torment emissions. In some systems, undesirable emissions even occur during the production and / or storage of the molds.
• inorganic binders are increasingly preferred for use in the foundry industry; There is a high technical and economic interest in further improving the product properties of the foundry molded bodies produced, in particular molds and cores.
• Inorganic binders have long been known, especially those based on water glasses.
• three different methods are available for curing the water glasses: (i) passing a gas, e.g. CO2, air or a combination of both; (ii) addition of liquid or solid hardeners, e.g. certain esters, and (iii) thermal curing, e.g. in the so-called hot box process or by microwave treatment.
• a gas e.g. CO2
• addition of liquid or solid hardeners e.g. certain esters
• thermal curing e.g. in the so-called hot box process or by microwave treatment.
• foundry moldings produced from inorganic binders relatively often have low strengths, unless suitable, special measures are taken. This is particularly evident immediately after the removal of the core or the mold or the molding from the tool come to light.
• the strengths at this time (“hot strength” or “instant strength”) are particularly important for the safe handling of the cores or molds upon removal from the tool.
• high so-called “cold strength” i.e., the strength after complete cure of the core or mold) is important to make the desired casting as possible without casting defects.
• Document DE-OS 2652421 describes binders which consist of a solution of a mixture of potassium silicate and / or sodium silicate with lithium silicate and are suitable, for example, as binders for foundry cores.
• the document US 4,347,890 describes a method for binding a particulate material. The method comprises mixing the particulate material with a solution containing lithium ions (according to Example 1, this is an aqueous solution of lithium silicate or lithium water glass), mixing sodium silicate into this mixture, and finally shaping the mixture and curing it by means of microwave radiation.
• the document WO 2006 / 024540A2 describes i.a. a method for the production of molds, wherein a proportion of a particulate metal oxide is added to a water glass-based binder.
• Document WO 2014 / 202042A1 describes lithium-containing molding mixtures based on an inorganic binder for the production of molds and cores for metal casting. There is e.g. described that by defined addition of lithium-containing compounds to inorganic binders based on water glass, the storage stability of cores or molds produced with such binders can be improved. At the same time said cores or molds should have a high level of strength.
• liquid, inorganic binders with a proportion of lithium ions in particular those based on water glass, depending on the lithium ion concentration contained therein as well as the storage conditions (in particular the storage temperature) become too unstable can.
• Such unstable binders for example, already form turbidity over the course of storage for a few days, for example due to the formation of gels, and / or exhibit a precipitation of solids, such as carbonates and / or silicates, thus becoming inhomogeneous or heterogeneous.
• Binder especially water glass
• a further object of the present invention was to provide an easy-to-handle kit which is suitable for producing a liquid, lithium-containing, inorganic binder with variably adjustable lithium ion concentration, the binder under the individual storage conditions at least until its intended use should be stable.
• An additional specific object of the present invention was to provide a plant, such as a production plant, which makes it possible to carry out the aforementioned process on an industrial production scale.
• the primary object and other objects and / or subtasks of the present invention are achieved by a process according to the invention for producing a molding material mixture or for producing a molding material mixture and a molding thereof, preferably a storage-stable molding, wherein the molding material mixture includes:
• (M1) a molding material and (M2) a solution or dispersion comprising lithium-containing water glass which has a molar modulus S1O2 / M2O in the range from 1.6 to 3.5, preferably in the range from 1.8 to 3.0, and in which the molar fraction of L12O at M2O in the range of 0.05 to 0.60, preferably in the range of 0, 1 to 0.4, comprising the following steps:
• Kit comprising at least the following separate components: (K1) an aqueous solution or dispersion comprising water glass, the content of S1O2 being in the range from 20 to 34% by weight, preferably in the range from 25 to 34% by weight .-%, based on the total mass of the solution or dispersion, and / or wherein the molar modulus S1O2 / M2O is greater than the molar modulus of the lithium-containing waterglass in the molding mixture to be prepared, and
• M2O each denotes the total amount of lithium, sodium and potassium oxide.
• the molar modulus S1O2 / M2O is greater than the molar modulus of the lithium-containing water glass in the molding mixture to be produced.
• the component (K1) being present as an aqueous solution or dispersion comprising water glass, the content of S1O2 being in the range from 20 to 34% by weight, preferably in the range from 25 to 34 wt .-%, based on the total mass of the solution or dispersion, and wherein the molar modulus S1O2 / M2O is greater than the molar modulus of the lithium-containing waterglass in the molding mixture to be prepared.
• a process according to the invention as described above in which the aqueous solution or dispersion comprising water glass (K1) has a pH in the range from 10.0 to 13.0, is preferred. preferably in the range of 1 1, 0 to 12.5.
• the first water-glass-free solution or dispersion comprising lithium ions (K2a) dissolved in water has a pH in the range of 8.0 to 14.0, preferably in the range of 1 1, 5 to 13.5.
• S1O2 means the amount of substance in moles of silicon in the aqueous solution or dispersion, calculated according to the empirical formula S1O2, regardless of whether the silicon on which this calculation is based is actually present as S1O2 in the process according to the invention (or the kit according to the invention)
• M represents an alkali metal selected from the group consisting of lithium, sodium and potassium.
• M2O means the total amount of substance in moles of alkali metal in the aqueous solution or dispersion, calculated according to the empirical formula M2O.
• Li20 accordingly means the amount of substance in moles of lithium, calculated according to the empirical formula L12O.
• component (K1) comprises an aqueous (water-containing) solution or dispersion comprising water glass.
• water glass is understood in the context of the present invention per se known alkali water glass, which solidified from a melt, glassy, so amorphous, water-soluble sodium, potassium and - in low concentrations, which does not affect the stability, in particular the storage stability of the water glass - Lithium silicates or aqueous solutions of the aforementioned sodium, potassium and lithium silicates.
• the molding material (M1) is preferably a particulate refractory molding material.
• "refractory” is understood to mean, in accordance with the usual expert understanding, masses, materials and minerals which can withstand for a short time the temperature load during casting or solidification of a molten metal, for example aluminum Quartz, zircon or chrome ore sand, olivine, vermiculite, bauxite, chamotte and artificial molding compounds
• the molding material (M1) may be a mixture of several (preferably particulate, refractory) materials.
• the molded article produced according to the process of the invention indicated above is preferably a shaped body to be used in the foundry industry, more preferably a mold or a core.
• a particular advantage of the invention The method is the possibility to use a binder system with high or variably adjustable content of lithium ions required for the production of moldings with high strength and high storage stability, which does not or to a much lesser extent limit the storage times of known binders with high (but in usually not changeable and / or intended for change) Lihi- ionionen content is subjected.
• moldings can be produced which have a high strength and can be stored for a long time, preferably a period in the range of one day to two weeks, without sacrificing their advantageous properties to a practically relevant extent.
• the molded articles produced by the process according to the invention can thus be easily handled after their production and until use in a casting operation without deforming or breaking and / or can be stored for a long period of time, so that production in stock is possible.
• Particularly advantageous is the property of the molded body produced by the process according to the invention to maintain their high strength even at elevated humidity and to remain stable, so that the moldings produced are characterized by a long shelf life even in humid or humid climates. But also for changing weather conditions (seasons) in temperate climates brings the inventive method advantages.
• component (K2a) comprises lithium ions dissolved in water. If the component (K2a) is a solution, the lithium ions are part of the solution. If the component (K2a) is a dispersion, the lithium ions are present at least predominantly and preferably completely in the continuous (liquid, aqueous) phase, preferably dissolved.
• the component (K2a) preferably also comprises sodium ions and / or potassium ions in addition to the lithium ions as further alkali metal ions.
• Component (K2a) may comprise lithium ions and potassium ions or component (K2a) may comprise lithium ions and sodium ions, or component (K2a) may comprise lithium ions, sodium ions and potassium ions.
• the maximum value of the total concentration of the lithium, sodium and potassium ions in the component (K2a) depends inter alia on the type and the proportion of the alkali metal ions present. The person skilled in the art knows how to adjust the required and / or preferred concentrations of alkali metal ions under the given or desired conditions.
• step (1) additionally comprises the following separate component:
• (K2b) a second water-glass-free solution or dispersion comprising alkali metal ions dissolved in water, preferably comprising lithium ions dissolved in water, the concentration of lithium ions being lower than in component (K2a) and preferably in the range from 0 to 5.0 mol / L , more preferably in the range of 0 to 2.0 mol / L, and the total concentration of lithium, sodium and potassium ions in the range of 0.3 to 28.0 mol / L, preferably in the range of 0.3 to 20.0 mol / L, particularly preferably in the range of 1, 0 to 10.0 mol / L, and preferably the total concentration of lithium, sodium and potassium ions is not more than 20%, preferably not more than 10%, of the
• step (2) comprises:
• the second water-glass-free solution or dispersion comprising lithium ions (K2b) dissolved in water has a pH in the range from 8.0 to 14.0, preferably in the range of 1 1, 5 to 13.5.
• preferred pH values for the solutions or dispersions (K1) and / or (K2a) reference is made to the disclosure above.
• (M2) a solution or dispersion comprising lithium-containing water glass which has a molar modulus S1O2 / M2O in the range from 1.6 to 3.5, preferably in the range from 1.8 to 3.0, and in which the molar fraction of U2O at M2O in the range of 0.05 to 0.60, preferably in the range of 0, 1 to 0.4, comprising the following steps:
• (K1) an aqueous solution or dispersion comprising water glass, the content of S1O2 being in the range from 20 to 34% by weight, preferably in the range from 25 to 34% by weight, based on the total mass of the solution or dispersion, and / or wherein the molar modulus S1O2 / M2O is greater than the molar modulus of the lithium-containing waterglass in the molding mixture to be prepared,
• component (K2b) comprises alkali metal ions dissolved in water, preferably lithium ions, sodium ions and / or potassium ions.
• the component (K2b) preferably comprises lithium ions.
• the component (K2b) may comprise as lithium ions only lithium ions or only sodium ions or only potassium ions.
• the component (K2b) may include, as alkali metal ions, also lithium ions and sodium ions, or may include lithium ions and potassium ions, or may include sodium ions and potassium ions.
• the concentration of lithium ions in component (K2b) is lower than in component (K2a) and is preferably in the range from 0.1 to 5.0 mol / L, more preferably in Range from 0.1 to 2.0 mol / L,
• the total concentration of lithium, sodium and potassium ions in the component (K2b) by not more than 20%, preferably not more than 10%, of the total concentration of lithium, sodium and Potassium ions in the component (K2a) deviates, it is achieved that when mixing the kit components (K1), (K2a) and (K2b) together (in the absence or presence of the molding material (M1)), the total concentration of lithium, sodium and potassium ions in the resulting solution or dispersion (M2) is equal to or at least similar to the total concentration of lithium, sodium and potassium ions in a solution or dispersion (M2) which is formed only by mixing the kit components (K1) and (K2a) together.
• the lithium ion concentration of the resulting solution or dispersion (M2) influenced, preferably reduced, compared to a solution or dispersion (M2) prepared by mixing only the kit components (K1) and (K2a) together and under otherwise identical conditions.
• the kit component (K2b) can thus be advantageously used to reduce the lithium ion content in a solution or dispersion (M2) in a readily metered and readily controllable manner, without the other properties of the resulting solution or dispersion (M2), for example its molar modulus SiC / I hO or their total concentration of alkali metal ions, to influence or change in a practically relevant way differently than would have been the case by addition of an appropriate amount of the kit component (K2a).
• the component (K2b) it is thus possible to ensure, when the addition of (K2a) is reduced, that the binder (M2) to be prepared has the same modulus and the same concentration as previously with a higher proportion of (K2a).
• step (2) of the above-mentioned preferred inventive method a mixture of the molding material (M1) with a proportion of the component (K1) and with a proportion of the component (K2a) and optionally with a proportion of the component (K2b) is prepared.
• the mixture described above can be prepared by first mixing a portion of component (K1) with the molding material (M1) and then mixing this premix with a proportion of component (K2a) and optionally with a proportion of component (K2b) to form a molding material mixture is mixed, wherein preferably the content of lithium ions in the molding material mixture by selecting component (K2a) and optionally component (K2b) is adjusted in each case a suitable amount and lithium ion concentration.
• the solution or dispersion (M2) is also formed.
• the mixture can also be prepared by first mixing the masterbatch (M1) with a portion of component (K2a) and optionally with a portion of component (K2b), and then mixing this masterbatch with a portion of component (K1) to form a masterbatch is, wherein preferably the content of lithium ions in the molding material mixture by selecting component (K2a) and optionally component (K2b) is adjusted in each case a suitable amount and lithium ion concentration.
• the solution or dispersion (M2) is also formed.
• the mixture is preferably prepared in step (2) of the process according to the invention by first adding a fraction of component (K1) with a fraction of component (K2a). and optionally with a proportion of component (K2b) to a solution or dispersion (M2) is mixed, wherein preferably the content of lithium ions in the solution or dispersion (M2) by selecting component (K2a) and optionally component (K2b) in each case appropriate amount and lithium ion concentration is adjusted.
• This separately prepared solution or dispersion (M2) is then mixed with the molding base (M1).
• the mixture is particularly preferably prepared in step (2) of the process according to the invention by first mixing a portion of component (K2a) with a portion of component (K2b) into a "premix (K2a) + (K2b)" and this "premix (K2a) + (K2b) "is then mixed with a proportion of component (K1) to a solution or dispersion (M2), wherein preferably the content of lithium ions in the solution or dispersion (M2) by selecting component (K2a) and Component (K2b) is adjusted in each case suitable amount and lithium ion concentration.
• (M1) a molding material and (M2) a solution or dispersion comprising lithium-containing waterglass having a molar modulus S1O2 / M2O in the range of 1.6 to 3.5, preferably in the range of 1.8 to 3.0, and in which the molar fraction of L12O on M2O is in the range from 0.05 to 0.60, preferably in the range from 0.1 to 0.4, with the following steps: (1) Making or Providing a Kit at least comprising the following separate components:
• (K1) an aqueous solution or dispersion comprising water glass, the content of S1O2 being in the range from 20 to 34% by weight, preferably in the range from 25 to 34% by weight, based on the total mass of the solution or dispersion, and / or wherein the molar modulus SiC / I hO is greater than the molar modulus of the lithium-containing waterglass in the molding mixture to be prepared,
• (K2b) a second water-glass-free solution or dispersion comprising lithium ions dissolved in water, wherein the concentration of lithium ions is lower than in the component (K2a) and preferably in the range of 0, 1 to 5.0 mol / L, more preferably in the range from 0.1 to 2.0 mol / L, and the total concentration of lithium, sodium and potassium ions in the range of 0.3 to 28.0 mol / L, preferably in the range of 0.3 to 20.0 mol / L, more preferably in the range of 1, 0 to 10.0 mol / L, and preferably the total concentration of lithium, sodium and potassium ions does not deviate by more than 20%, preferably not more than 10%, from the total concentration of lithium, sodium and potassium ions in the component (K2a), and thereafter
• step (2) first a solution or dispersion (M2) is formed by mixing the components of the kit used together in the absence of the molding base material and thereafter a mixture of the or a fraction of the masterbatch (M1) is formed with a proportion or the total amount of the obtained solution or dispersion (M2).
• M2 a solution or dispersion
• M1 a mixture of the or a fraction of the masterbatch
• premixed solution or dispersion (M2) can be prepared and then stored for a certain period, preferably so to the ambient conditions It is (or may be) adapted to prevent precipitation (due to solvent or dispersion component failure (M2)) and / or gelation due to instabilities, such premixed solution or dispersion (M2) can also be used to feed an automated or semi-automated production facility, so that the premixed solution or dispersion (M2) can be used directly in a serial or predominantly serial industrial production.
• M2 premixed solution or dispersion
• M2 pre-mixed solution or dispersion
• the solution or dispersion prepared (M2) prior to forming the mixture with the masterbatch (M1) contains no visible precipitates or gel fractions.
• M2 solution or dispersion prepared
• M1 contains no visible precipitates or gel fractions.
• Said test is preferably carried out directly before producing a mixture of the molding material (M1) with the prepared solution or dispersion (M2) for producing a molding material mixture. If the test shows that the prepared solution or dispersion (M2) does not have the consistency or quality required for further processing, this is not used in further process steps. but preferably replaced by another solution or dispersion (M2), which has the consistency or quality required for further processing.
• This process design makes it possible to carry out a quick, simple and cost-effective quality control in the manufacturing plant.
• a method according to the invention as described above in particular a method which is referred to as preferred above or below, preferably a method variant comprising premixing of the kit components used
• mixing the components of the kit used together to form the solution or dispersion (M2) takes place in a mixing device, wherein preferably the mixing device is a metering container or a mixing tube and is preferably a mixing tube, particularly preferably a static mixing tube.
• the mixing device may be a separate mixing device operated approximately independently of or at least partly by serial production of shaped bodies ("discontinuous operation") .
• This discontinuous operation has the advantage that different batches of solutions or dispersions (M2
• the mixing device can also be part of an at least partially serial production of moldings, for example part of a plant for the at least partially serial production of moldings ("continuous or semi-continuous operation").
• continuous or semi-continuous operation is particularly suitable for the (industrially preferred) at least partially serial production of larger numbers of moldings, for example a production in stock.
• the mixing device may also be a storage container in which at least one of the components (K1), (K2a) and / or (K2b) is stored or reserved for use in an at least partially serial production of moldings and in which at least one complementary Component (K1), (K2a) and optionally (K2b) is admixed.
• the above-mentioned mixing device is preferably a metering container or a mixing tube.
• a static mixing tube is preferred.
• a static mixing tube is a mixing device which is particularly preferred for use in the method according to the invention. Suitable for use in the process according to the invention are, for example, static mixing tubes of the company. Sulzer, for example of the type "CompaX TM" or "SMX TM plus”.
• Preferred dosing containers are selected from the group consisting of "intermediate bulk containers” (also referred to as “IBC containers” or “contactor containers”), drums and canisters
• IBC containers intermediate bulk containers
• drums drums and canisters
• a preferred mixing device for the aforementioned continuous or semi-continuous operation is a mixing tube, preferably A static mixing tube can also be used in continuous or semi-continuous operation.
• a process according to the invention as described above is also preferred (in particular a process which is referred to as preferred above or below, preferably a process variant comprising premixing of the kit components used), the proportion or the total amount of the solution or dispersion formed (M2 ) is stored in the mixer for a period of not more than 7 days, preferably not more than 3 days, more preferably not more than 2 days, prior to the formation of a mixture with or a portion of the masterbatch (M1).
• the formation of precipitates by failure of components of the solution or dispersion (M2)
• / or gels counteracted.
• the mixing device is part of an at least partial serial production of moldings
• prolonged storage of the prepared solution or dispersion (M2) such as storage for a period of more than 2 days, preferably over a period of more than a day, usually not provided. Instead, in these cases, usually a shorter storage is provided for preferably not more than one day, so that an at least partially serial production or such a production process is possible.
• prolonged storage (preferably for the above-defined period of not more than seven days) of the prepared solution or dispersion (M2) may be preferred in cases where the mixer is also used as a reservoir for a prepared solution or dispersion (M2) prior to Mixing with the molding material (M1) is used.
• a process according to the invention as described above (in particular a process which is referred to above or below as preferred) for producing a molding material mixture and a molding thereof, with the additional steps, is preferred
• Particularly preferred is a combination of a parameter from the group of ambient temperature in the production of the shaped body and temperature during storage of the shaped body with a parameter from the group relative humidity in the production of the molding and relative humidity during storage of the molding.
• the "relative humidity” indicates - in accordance with the usual understanding of the skilled person - at a given temperature, the actual water content in the air, based on the at this temperature physical maximum of the water content of the air.
• Absolute humidity is determined from temperature and relative humidity, in accordance with the usual understanding of the skilled person. Higher absolute humidity is achieved if, for example, the temperature rises while the relative humidity remains the same or if the relative humidity increases while the temperature remains the same. Factors which make the setting of a comparatively higher concentration of lithium ions appear sensible in the process according to the invention are in particular a higher absolute humidity in the production and / or storage of a molded article and / or a longer storage life of the molded article. Accordingly, depending on the set, determined or estimated parameter value, preferably a higher or a lower concentration of lithium ions in the solution or dispersion (M2) is set.
• a higher concentration of lithium ions can preferably be adjusted by increasing the proportion of component (K2a) in the solution or dispersion (M2), for example by increasing the proportion of admixture of component (K2a) and / or (if component (K2b ) is used) by reducing the proportion of admixture of the component (K2b).
• the component (K2b) can also be omitted altogether, depending on the requirements.
• a method according to the invention as described above is preferred, wherein the method is designed as at least partially serial, preferably as a predominantly serial, production of a number of moldings or expected increase of one or more parameters selected from the group consisting of ambient temperature in the production of the molding, relative humidity during the production of the molding, temperature in the storage of the molding, relative humidity during storage of the molding
• a method according to the invention as described above (in particular a method which is referred to as preferred above or below), wherein for setting, determining or estimating the one or more parameters selected from the group consisting of ambient temperature in the production of the shaped body, Relative humidity in the production of the molding, temperature during storage of the molding, relative humidity during storage of the molding, absolute humidity in the production of the molding, absolute humidity during storage of the molding and storage life of the molding a data acquisition device or data processing device is provided and Controlling the components to be used of the components (K2a) and (K2b) depending on the one or more adjusted, determined or estimated parameters, a control device is provided, wherein preferably between the data acquisition device or the data processing device and the control device, a data connection for the transmission of parameter data is set up.
• the aforementioned data acquisition device or data processing device is preferably an instrument for detecting the climatic conditions or a data logger.
• the aforementioned control device is preferably an automated mixing device.
• This aforementioned embodiment of the method according to the invention has the advantage that the admixture or metering of the kit components can be carried out automatically or at least partially automatically as a function of the influencing parameters in an industrial production process.
• a process according to the invention is also preferred as described above (in particular a process which is referred to above or below as preferred), in which case one or more constituents are additionally added when preparing the molding material mixture, which are selected from the group consisting of:
• M3 particulate, amorphous silica; barium sulfate; Carbohydrates; Phosphorus compounds; surface-active compounds; oxidic boron compounds; Metal oxides; Lubricants, esters and release agents.
• particulate, amorphous silica As particulate, amorphous silica ("S1O2”) it is preferred to use particulate, amorphous silica in conventional purity, ie with conventional impurities and minor constituents
• particulate amorphous silica having a content of at least 85% by weight is used. %, particularly preferably of at least 90% by weight and very particularly preferably of at least 95% by weight of silica
• the term "particulate” designates a solid powder (including dusts) or also a granulate which is preferably pourable and thus also is sievable.
• the particle number-related d90 value of the particulate, amorphous silicon dioxide is less than 100 ⁇ m, particularly preferably less than 45 ⁇ m.
• 90% of the particles of the particulate, amorphous silicon dioxide contained in the molding material mixture are preferably smaller than 100 ⁇ m, preferably smaller than 45 ⁇ m.
• the d90 value is preferably determined by taking pictures with the scanning electron microscope.
• a particulate, amorphous silica both synthetically produced and naturally occurring types can be used. The latter are known, for example, from the document DE 102007045649, but are not preferred because they often contain not inconsiderable crystalline components and are therefore classified as carcinogenic.
• Synthetically produced particulate amorphous silica is produced by a deliberate chemical reaction. Examples include the flame hydrolysis of silicon tetrachloride and the reduction of silica sand with coke in the electric arc furnace in the production of ferrosilicon and silicon.
• the amorphous S1O2 prepared by these two methods is also referred to as "pyrogenic S1O2.”
• Another example of synthetically produced particulate amorphous silica is silicon dioxide obtained by thermal decomposition of ZrSiC to ZrZ2 and S1O2 and partial or essentially complete removal of ZrO2, as described, for example, in document DE 102012020509.
• component (M3) synthetic, particulate, amorphous SiO 2 is used according to the process of the invention , particularly preferably pyrogenic particulate, amorphous S1O2 and / or S1O2 from the thermal decomposition of ZrSiC.
• Particulate amorphous silica suitable for the purposes of the present invention is also indicated, for example, in the documents DE 102004042535A1, DE 102012020510A1 and DE 10201202051 1A1.
• the particulate, amorphous silica is used in an amount in the range of 0.3 to 3.0 wt .-%, based on the total weight (the total mass) of the molding material mixture (sum of the weights or masses of the ingredients (M1), (M2) and - if available - (M3) and other optional components).
• barium sulfate synthetic or natural barium sulfate, i. in the form of minerals containing barium sulfate, such as barite or barite.
• Synthetically produced barium sulfate (also known as “blanc fixe") is produced, for example, by a precipitation reaction, in which sparingly soluble barium compounds (barium salts) are dissolved in water, followed by the addition of slightly soluble sulfate salts (such as sodium sulphate) The precipitated barium sulphate is filtered off, dried and optionally ground.
• barium sulphate suitable for the purposes of the present invention is also disclosed in document DE 102012104934.
• the barium sulphate is added in an amount in the range from 0.02 to 5, 0 wt .-% used, based on the total weight (the total mass) of the molding material mixture (sum of the weights or masses of the components (M1), (M2) and - if present - (M3) and optionally further constituents).
• the carbohydrates which can be used as or in component (M3) in the method according to the invention described above are preferably selected from the group consisting of oligosaccharides and polysaccharides, preferably selected from the group consisting of cellulose, starch and dextrin.
• the carbohydrates mentioned can be used individually or in combination with one another.
• Carbohydrates suitable for the purposes of the present invention are also given, for example, in document EP 2104580.
• the carbohydrate (s) are used in an amount in the range from 0.01 to 10.0% by weight, based on the total weight (the Total mass) of the molding material mixture (sum of the weights or masses of the constituents (M1), (M2) and - if present - (M3) and optionally further constituents).
• the phosphorus compounds which can be used as or in component (M3) in the process according to the invention described above are preferably selected from the group consisting of organic phosphates and inorganic phosphates, preferably selected from the group consisting of inorganic alkali metal phosphates.
• the phosphorus compounds mentioned can be used individually or in combination with one another. Phosphorus compounds which are suitable for the purposes of the present invention are also mentioned, for example, in document EP 2097192.
• the phosphorus compound (s) is used in an amount in the range from 0.05 to 1.0% by weight, based on the total weight ( the total mass) of the molding material mixture (sum of the weights or masses of the constituents (M1), (M2) and - if present - (M3) and optionally further constituents).
• the surface-active compounds which can be used as or in component (M3) in the process according to the invention described above are preferably selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants.
• the surfactants mentioned can be used individually or in combination with one another.
• Surfactants suitable for the purposes of the present invention are also mentioned, for example, in document DE 102007051850.
• the surface-active compound (s) is used in an amount in the range from 0.001 to 1.0% by weight, based on the total weight (the total mass ) of the molding material mixture (sum of the weights or masses of the constituents (M1), (M2) and - if present - (M3) and optionally further constituents).
• the aforementioned surface-active compounds can also be used as a constituent of component (K1).
• the oxidic boron compounds which can be used as or in constituent (M3) in the process according to the invention described above are preferably selected from the group consisting of borates, boric acids, boric anhydrides, borosilicates, borophosphates and borophosphosilicates, more preferably selected from the group consisting of alkali metal and Erdalkaliborat, wherein preferably the oxide boron compound does not contain organic groups.
• the oxide boron compounds mentioned can be used individually or in combination with one another. For the purposes of this Oxidic boron compounds suitable for the invention are also disclosed, for example, in document DE 1020131 1 1626.
• the oxide boron compounds are or are used in an amount in the range from 0.001 to 1.0% by weight, based on the total weight (the total mass) of the molding material mixture (Sum of the weights or masses of the constituents (M1), (M2) and - if present - (M3) and optionally further constituents).
• the abovementioned oxidic boron compounds can also be used as constituent of component (K1).
• the metal oxides usable as or in component (M3) in the process according to the invention described above preferably comprise particulate mixed metal oxides, preferably comprising oxides of aluminum and / or oxides of zirconium.
• Preferred metal oxides include particulate alumina, preferably in the alpha phase, and / or particulate aluminum / silicon mixed oxide without a layered silicate structure.
• the metal oxides mentioned can be used individually or in combination with one another.
• Metal oxides suitable for the purposes of the present invention are also given, for example, in the documents DE 1020121 13074 and DE 1020121 13073.
• the metal oxide (s) are used in an amount in the range from 0.05 to 8.0% by weight, based on the total weight (the total mass) of the molding material mixture (sum of the weights or masses of the constituents (M1), (M2) and - if present - (M3) and optionally further constituents).
• the lubricants which can be used as or in component (M3) in the process according to the invention described above are preferably selected from graphite and / or molybdenum (IV) sulfide.
• the aforementioned lubricants can be used individually or in combination with each other.
• lubricants suitable for the purposes of the present invention are also given in document WO 2014/202042.
• the lubricant or lubricants are used in an amount in the range of 0.01 to 0.2 wt .-%, based on the total weight (the total mass) of the molding material mixture (sum of the weights or masses of the ingredients (M1) , (M2) and - if available - (M3) and, where appropriate, other constituents).
• silanes which can be used as or in component (M3) in the process according to the invention described above are preferably selected from the group consisting of aminosilanes, epoxysilanes, mercaptosilanes, hydroxysilanes and ureidosilanes.
• the aforementioned silanes can also act as a lubricant.
• the silanes mentioned can be used individually or in combination with one another.
• silanes suitable for the purposes of the present invention are also given in document WO 2014/202042.
• the silane or silanes are used in an amount in the range of 0.1 to 2.0 wt .-%, based on the total weight (the total mass) of the molding material mixture (sum of the weights or masses of the components (M1), ( M2) and - if present - (M3) and optionally other constituents).
• the release agents which can be used as or in component (M3) in the process according to the invention described above are preferably selected from the group consisting of calcium stearate, fatty acid esters, waxes, natural resins and alkyd resins. The release agents mentioned can be used individually or in combination with one another. Parting agents suitable for the purposes of the present invention are also disclosed, for example, in document EP 1802409.
• the release agent (s) are used in an amount in the range of from 0.1 to 2.0% by weight, based on the total weight (i.e. Total mass) of the molding material mixture (sum of the weights or masses of the constituents (M1), (M2) and - if present - (M3) and optionally further constituents).
• esters (one or more) which can be used as or in component (M3) in the process according to the invention described above are preferably selected from the group consisting of the intramolecular or intermolecular reaction products of an alcohol and an acid, where the alcohol is selected from the group consisting of C1 -C8 mono-alcohols, C1-C8 di-alcohols, preferably C2-C8 di-alcohols, and C1-C8 tri-alcohols, preferably C3-C8 tri-alcohols, preferably selected from the group consisting of ethylene glycol, 1, 2 Propanediol and glycerol, and wherein the acid is selected from the group consisting of organic C 1 -C 8 mono-carboxylic acids, preferably organic C 2 -C 8 mono-carboxylic acids, organic C 2 -C 8 di-carboxylic acids, organic C 2 -C 8 tri-carboxylic acids , Preferably organic C3-C8 tri-carboxylic acids
• esters can be used individually or in combination with one another.
• the ester or esters are used in an amount of up to 0.4% by weight, preferably in an amount in the range of 0.01% to 0.4% by weight, based on the Total weight (the total mass) of the molding material mixture (sum of the weights or masses of the constituents (M1), (M2) and - if present - (M3) and optionally further constituents).
• the aforementioned one or more components (M3) - particulate, amorphous silica; barium sulfate; Carbohydrates; Phosphorus compounds; surface-active compounds; oxidic boron compounds; Metal oxides; Lubricants, esters and release agents - may be used alone or in combination with each other.
• the one or more constituents (M3) can be added, for example, individually or jointly, preferably together, to the molding base material (M1) and mixed with it, and then the prepared (premixed) can be added to this premix of components (M1) and (M3) ) Solution or dispersion (M2) are added and mixed with it (preferably homogeneously).
• the first water-glass-free solution or dispersion (K2a) and optionally (if present or used) the second water-glass-free solution or dispersion (K2b) each comprises lithium hydroxide dissolved in water.
• the first water-glass-free solution or dispersion comprises lithium ions (K2a) dissolved in water and lithium hydroxide dissolved in water.
• the second water-glass-free solution or dispersion comprising alkali metal ions (K 2 b) dissolved in water comprises lithium ions
• the second water-glass-free solution or dispersion comprises lithium hydroxide dissolved in water.
• Lithium hydroxide, especially lithium hydroxide monohydrate, has a water solubility suitable for the purposes of the present invention.
• lithium hydroxide in particular lithium hydroxide monohydrate
• solutions or dispersions (K2a) or (K2b) can be prepared with excellent storage stability.
• lithium hydroxide more preferably lithium hydroxide monohydrate.
• a method according to the invention as described above in particular a method according to the invention, which is referred to in this text as being preferred), wherein
• the aqueous solution or dispersion comprising water glass (K1) has a pH in the range from 10.0 to 13.0, preferably in the range from 11.0 to 12.5, and / or (preferably "and")
• the first water-glass-free solution or dispersion comprising lithium ions (K2a) dissolved in water has a pH in the range of 8.0 to 14.0, preferably in the range of 11.5 to 13.5, and / or (preferably "And” if component (K2b) is present)
• the second water-glass-free solution or dispersion comprising dissolved in water lithium ions (K2b) (if used) has a pH in the range of 8.0 to 14.0, preferably in the range of 1 1, 5 to 13.5.
• the invention also relates to a kit for preparing a solution or dispersion comprising lithium-containing waterglass, at least comprising the following separate components:
• (K1) an aqueous solution or dispersion comprising water glass, the content of S1O2 being in the range from 20 to 34% by weight, preferably in the range from 25 to 34% by weight, based on the total mass of the solution or dispersion, and / or wherein the molar modulus SiC / I bO is greater than the molar modulus of the lithium-containing water glass to be produced, and
• kit according to the invention described above additionally comprising as another separate component:
• (K2b) a second water-glass-free solution or dispersion comprising alkali metal ions dissolved in water, wherein the concentration of lithium ions is lower than in component (K2a) and preferably in the range of 0 to 5.0 mol / L, particularly preferably in the range of 0 to 2.0 mol / L, and the total concentration of the lithium, sodium and potassium ions in the range of 0.3 to 28.0 mol / L, preferably in the range of 0.3 to 20.0 mol / L, particularly preferred in the range of 1.0 to 10.0 mol / L, and preferably the total concentration of the lithium, sodium and potassium ions is not more than 20%, preferably not more than 10%, of the total concentration of the lithium, Sodium and potassium ions in the component (K2a) deviates.
• the concentration of lithium ions in the component (K2b) is lower than in the component (K2a) and is preferably in the range of 0.1 to 5.0 mol / L, more preferably in Range of 0.1 to 2.0 mol / L.
• kits according to the invention comprising at least the following separate components: (K1) an aqueous solution or dispersion comprising water glass, wherein the content of S1O2 in the range of 20 to 34 wt .-%, preferably in the range of 25 to 34 wt .-%, based on the total mass of the solution or dispersion , and / or wherein the molar modulus S1O2 / M2O is greater than the molar modulus of the lithium-containing waterglass to be produced,
• (K2b) a second water-glass-free solution or dispersion comprising lithium ions dissolved in water, wherein the concentration of lithium ions is lower than in the component (K2a) and preferably in the range of 0, 1 to 5.0 mol / L, particularly preferably in the range of 0, 1 to 2.0 mol / L, and the total concentration of lithium, sodium and potassium ions in the range of 0.3 to 28.0 mol / L, preferably in the range of 0.3 to 20.0 mol / L L, more preferably in the range of 1, 0 to 10.0 mol / L, and preferably the total concentration of the lithium, sodium and potassium ions by not more than 20%, preferably not more than 10%, of the Total concentration of lithium, sodium and potassium ions in the component (K2a) deviates.
• the invention also relates to the use of a above-described inventive or preferred inventive kit for producing a molding material mixture or for producing a molding material mixture and a molding thereof, wherein the molding material mixture comprises:
• (M2) a solution or dispersion comprising lithium-containing water glass which has a molar modulus S1O2 / M2O in the range from 1.6 to 3.5, preferably in the range from 1.8 to 3.0, and in which the molar fraction of L12O to M2O is in the range of 0.05 to 0.60, preferably in the range of 0, 1 to 0.4.
• the invention further relates to a plant for use in the production of a molding material mixture or for producing a molding material mixture and a molding thereof (preferably for use in the preparation according to a method of the invention), preferably for the preparation of an intermediate solution or dispersion comprising lithium-containing water glass for use in the production of a molding material mixture or for producing a molding material mixture and a molded article thereof, the plant comprising at least: a first storage tank (Z1) containing as the first component an aqueous solution or dispersion (K1) comprising water glass, wherein the Content of S1O2 in the range of 20 to 34 wt .-%, preferably in the range of 25 to 34% by weight, based on the total mass of the solution or dispersion, and / or wherein the molar modulus SiCte / I hO is greater as the molar module of the lithium-containing waterglass in the molding mixture to be produced, a second storage tank (Z2) containing as second component a first water-glass-free solution or
• the plant according to the invention preferably comprises a mixing device (Z3) and preferably at least the first and the second storage tank are connected to the mixing device (Z3) in each case by one or more lines (Z4).
• the plant according to the invention is a plant for producing an intermediate solution or dispersion comprising lithium-containing water glass (with reference to the process according to the invention, this intermediate solution or dispersion is referred to as (M2)) for use in the preparation of a molding material mixture or for producing a Formstoffmischung and a molded article thereof.
• the invention also includes a plant described above, which does not require mixing device and in which the components (K1), (K2a) and - if present and used - (K2b), directly into the mold base material (M1) passed and only then mitei- and mixed with the molding base (M1).
• the mixing device (Z3) can simultaneously be a storage tank ((Z1), (Z2) or (Z5), see below).
• the contents of the storage tank (s) may be conveyed to the mixing device by means of one or more pumps.
• the components (K1), (K2a) and (K2b) can also be premixed in only one of the provided storage tanks and then mixed with the molding material. It can also only the components (K1) with (K2a) or optionally (K1) with (K2b) or (K2a) with (K2b) premixed in a storage tank and only then with the respective third component ((K2b) or (K2a) or (K1)) are mixed. It is also possible for the components (K1), (K2a) and (K2b) in each case to be mixed directly with the molding base material without mixing with one of the other components.
• kit according to the invention is suitable for and intended for use in the plant given above or below.
• a plant according to the invention as described above comprising a third storage tank (Z5) comprising a second water-glass-free solution or dispersion (K2b) comprising alkali metal ions dissolved in water, where o the concentration of lithium ions is lower than in the component (K2a) and preferably in the range of 0 to 5.0 mol / L, more preferably in the range of 0 to 2.0 mol / L, and o the total concentration of lithium, sodium and potassium ions in the range of 0.3 to 28.0 mol / L, preferably in the range of 0.3 to 20.0 mol / L, more preferably in the range of 1, 0 to 10.0 mol / L, and o preferably the total concentration of lithium, sodium and potassium ions by not more than 20%, preferably not more than 10%, differs from the total concentration of lithium, sodium and potassium ions in the component (K2a), wherein preferably the mixing device (Z3) is designed for mixing at least the first, second and third components, for
• the concentration of lithium ions in the component (K2b) in the third storage tank (Z5) is lower than in the component (K2a) and is preferably in the range of 0.1 to 5.0 mol / L, more preferably in the range of 0.1 to 2.0 mol / L.
• FIG. 1 shows a schematic structure of a section of a system according to the invention with the installation parts: a first storage tank (Z1), a second storage tank (Z2), a mixing device (Z3) and one or more (here: several) lines (Z4 ) connecting the first and second storage tanks to the mixing device.
• 2 shows a schematic structure of a section of a system according to the invention with the installation parts: a first storage tank (Z1), a second storage tank (Z2), a mixing device (Z3) (identical here to the first storage tank (Z1)) and one or more (here: one) lines (Z4), which connect the first and the second storage tank with the mixing device (wherein the first storage tank and the mixing device are identical).
• FIG. 3 shows a schematic structure of a section of a system according to the invention with the installation parts: a first storage tank (Z1), a second storage tank (Z2), a third storage tank (Z5), a mixing device (Z3) and one or more (Here: several) lines (Z4), which connect the first, the second and the third storage tank with the mixing device.
• Example 1a Exemplary Components (KD, (K2a) and (K2b)
• Exemplary components (K1), (K2a) and (K2b) were prepared in a manner known per se, with the properties shown in Table 1a.
• Table 1a Exemplary components (K1), (K2a) and (K2b)
• Table 1 b pH values of preferred components (K1), (K2a) and (K2b)
• Exemplary solutions or dispersions (M2) comprising lithium-containing waterglass according to the process of the invention are prepared by mixing components (K1), (K2a) and optionally (K2b) known per se, with one another. In each case, the components specified in Example 1 are used. For this purpose, the respective proportion of the component (K1) is presented and the respective proportion of the components (K2a) and optionally (K2b) added. By shaking or stirring, the resulting solutions or dispersions (M2) are homogenized. The results are shown in Table 2.
• composition of solutions or dispersions (M2) prepared according to the invention comprising lithium-containing waterglass
• a comparative molding mixture (VF1) was prepared from the constituents specified in Table 4 by the process according to the invention (molding material blends EF1 to EF3) and by a conventional, noninventive process, as specified below working procedure. All quantities in Table 4 are given in parts by weight.
• the "binders” (see Table 4) used were the inventive solutions or dispersions prepared according to Table 3, comprising lithium-containing waterglass (M2) or the noninventive solution or dispersion (M2v) (see binders EL1 to EL3 and VL1).
• quartz sand H31 from Quarzwerke GmbH, Frechen
• the additive used in each case was the commercial powdery additive for foundry moldings Anorgit® 8610 (Huttenes-Albertus Chemische Limited liability company), which contains, among other things, particulate, phes silicon dioxide.
• the molding material mixtures were each introduced by means of compressed air (4 bar) in the mold, (core box temperature 180 ° C).
• the firing time was 3 s, followed by a hardening time of 30 s (delay time 3 s).
• hot air (2 bar gassing pressure, 180 ° C. gassing and gassing hose temperature) was passed through the mold during the 30 s curing time.
• test specimens produced are molded bodies and, as is customary in the field in question, are modeled for moldings or cores which can be used in the foundry industry.
• the storage stability of water-glass-bonded moldings depends on the ambient conditions, especially on the humidity.
• the higher the humidity the higher the risk of damaging the molded article (e.g., nuclear damage). Damage to the shaped article is evident, e.g. by a component failure (e.g., core failure) or a large decrease in strength (low residual strength in terms of cold strength).
• a component failure e.g., core failure
• a large decrease in strength low residual strength in terms of cold strength
• At high humidity there is also a water absorption, which can lead to gas defects (eg gas bubbles in the casting) during the casting process.
• test specimens are in Table 5 (see column "Experiment") in each case characterized by the molding mixtures used for their preparation (see Example 3 and Table 3).
• test specimens were stored in the climatic chamber and the time to break was observed.
• the respective times in hours are given in Table 5 in each case as the mean value of 3 measurements.
• test specimens were stored for a certain period of time (see Table 5) in the climatic chamber.
• the flexural strengths were then measured immediately after removal from the climatic chamber.
• the test specimens prepared in Example 4 were placed in a Georg Fischer strength tester equipped with a 3-point bending device (company Multiserw) and the force was measured, which led to the fracture of the test specimens.
• the flexural strengths were measured after the times indicated in Table 5.
• the moldings (test specimens) are in Table 5 (see column "test") characterized in each case by the molding mixtures used for their preparation (see Example 3 and Table 4).
• the measured values obtained are given in Table 5 as the mean value of 3 measurements each.
• the indication "rLF” means the relative humidity and the indication “nb” means "not determined” (ie, no reading was determined).
• a suitably flexibly adjustable lithium ion concentration in a solution or dispersion (M2) to be prepared is advantageous because the desired properties of moldings, in particular the desired storage properties of moldings bound with binders, are specifically controlled or adjusted can:
• Components (K1), (K2a) and (K2b) of a solution or dispersion (M2) were used and mixed with each other and with the mold base material (M1) in the manner indicated below and under otherwise constant conditions by a process according to the invention : a) Components (K1), (K2a) and (K2b) were mixed directly without premixing with the molding material. b) Components (K1), (K2a) and (K2b) were premixed and the masterbatch was mixed directly with the masterbatch.
• prepared solutions or dispersions (M2) with a favorable (high) lithium content can therefore be pre-mixed for a short time and, if appropriate, in the medium term and used in industrial practice.
• homogeneous (e.g., premixed) solutions or dispersions (M2) with a favorable (high) lithium content are not suitable for the aforementioned reasons.
• Such solutions or dispersions (M2) with a favorable (high) lithium content should therefore according to the subject matter of the present invention only in the short or medium term before the actual industrial use by mixing separately stored components (K1), (K2a) and optionally (K2b) with each other, or mixed with a molding material to a molding material mixture.

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