巴西专利BR112013032506B1 process for building layered models

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专利摘要:
PROCESS FOR BUILDING LAYER MODELS. The present invention relates to a process for the construction of layered models, where in a construction sector a particulate material is applied in layers and selectively hardened. These steps are repeated until a desired model is obtained. The material comprises, in this case, a particulate construction material and a spray dried alkali metal silicate solution. A selective activation of the hardening is carried out by means of a solution comprising water.
公开号:BR112013032506B1
申请号:R112013032506-2
申请日:2012-06-20
公开日:2020-11-03
发明作者:Ingo Gnüchtel；Daniel Günther；Ingo Ederer；Christian Lustig；Edgar Müller
申请人:Hüttenes-Albertus Chemische Werke GmbH；
IPC主号:

专利说明:

[001] The present invention relates to a process for the construction of layered models, as well as to systems of materials for the construction of layered models according to the concepts of claims 1 and 2.
[002] Generative processes for the production of 3D structures have been known for a long time (for example, from EP 0 431 924 B1 or from WO200168375A2).
[003] These include, among others, stereolithography processes (fixation of monomeric liquids with a high energy beam), selective laser sintering (smelting of particulate material with a high energy beam) and the 3D printing process. All the mentioned processes allow the comparative economic production of molds for the construction of prototypes. The 3D printing process also allows, when printing devices with multiple activable injectors are used, construction speeds higher than all other processes. As a result, the application is not limited to the prototype sector only. Even series components can be produced economically.
[004] From the state of the art, fundamentally different processes can be deduced: systems, which work completely on the basis of liquid and systems, which use powdered materials, which are selectively fixed through the liquid inlet or energy inlet.
[005] The purely liquid-based systems mentioned above are known, for example, from US 6,259,962 to Fa. Objet Geometries Ltd. This process is based on the fact that when fixing two different materials are generated. The layered model, after the printing process, can be released from the support material through a dissolution process - for example, a water bath
[006] The fixation of the materials initially supplied in liquid form for printing, can be carried out, for example, through UV radiation. In addition, systems of two or more components can be used, which are joined on the construction platform and fixed. Since the complete build volume has to be produced using inkjet printers, this process, however, is comparatively slow and is therefore only suitable for smaller components.
[007] An essentially more economical alternative, especially with respect to the intensity of time, forms the processes for the construction of layered models, which use particulate material. In these processes, a pulverized material is selectively bonded. The particulate material is applied, for example, with a thin layer coating machine on a workpiece platform and smoothed. A printhead, based on construction data deposited in a computer, fixes selective regions in the dust layer. This procedure is always repeated, until the component is finished and it can be removed from the non-fixed particulate material.
[008] An advantage in this case is that part of the component material is already supplied by the volume of the particulate material. The quantity, which must be dosed in a fluid form using a printer, is therefore comparatively small. In this way, this process allows for high printhead speeds, low layer times, and a comparatively simple printhead assembly.
[009] The fixation of the particulate material is performed, here, by gluing each of the particles together.
[0010] Inorganic binder systems have been used in the metal foundry industry since the middle of the last century to produce sand molds.
[0011] In this way, for example, so-called hydraulic adhesives are mentioned here, therefore, adhesives, which harden both in the air and under water.
[0012] Among these are, for example, materials for molds connected with plaster. For the production of foundry molds, for example, particulate material containing plaster is used. The plaster contained in the particulate material is activated with an aqueous solution and hardened, for example, selectively. The mold must be dried after printing.
[0013] After production, the plaster contains a lot of free water, which can lead to problems in the foundry, since it can escape abruptly when heated.
[0014] Furthermore, it has been shown that the strength of the plaster is not particularly high and the resistance of the plaster to temperature allows only a light metal casting for the resulting molds. In addition, it has been shown that gypsum in the hardened state is very dense and for gases, which can form in the smelter, it is only hardly permeable, which is why the gases can penetrate the melt.
[0015] In addition, materials for cement-linked molds are also known, here reference should be made, for example, to DE 10 2004 014 806 B4 and EP 1.510.310 A2.
[0016] Here, the cement is found in the sand for the casting mold and the cement is activated through an aqueous paint.
[0017] As a disadvantage, it was demonstrated here that cements, when heated, generally develop greater resistance, which they continue to maintain, also after cooling. This means that the casting can only be released from the mold material after casting.
[0018] In addition, too much water here can again lead to problems during casting. Therefore, the mold must be dried before casting.
[0019] In addition, it may also be that the distribution of reactive cement grains forms a problem in conventional layer production devices in 3D printing. Cements are often of low fluidity and tend to form agglomerates. This results in poor surface and component failures. In addition, due to the fine grain, they result in unpleasant powders. The unbound powder in the construction container is strongly alkaline and therefore unpleasant for the skin.
[0020] In addition to hydraulic adhesives, so-called crystal forming agents for use in mold materials are also known.
[0021] These include, for example, mold materials bound with salt, where sands can be mixed or coated with salts and the particulate material is printed with a solvent - as a rule, with an aqueous solution. In this case, the salt dissolves and forms bridges between the particles. After drying the mold, the water evaporates and fixes the connection.
[0022] Salt-bound mold materials have the advantage that after casting, they can be removed "wet", in which the casting parts are immersed in a water bath. The salt dissolves, the sand loses its connection and can be rinsed.
[0023] In the salt, however, after drying, water components are attached, which can be released in the casting of the mold, which can lead again to the gas problems already mentioned above.
[0024] In addition, the dimensional stability of the cores is relatively low, since salt tends to absorb moisture from the air and thereby softens.
[0025] Drying after printing can be controlled exactly, since too strong drying leads to loss of connection again. Too low drying again leads to gas problems in the casting.
[0026] Salts in sand are often aggressive towards metals, so that materials, which come into contact with sand, must be correspondingly passivated.
[0027] The use of mixtures of molded semi-products bonded with cement, plaster and salt is of no essential importance in series casting, in particular in car casting.
[0028] In addition, it is also generally known that soluble glass can be used as an adhesive for the production of foundry molds.
[0029] EP 2.163.328 A1 is known, for example, a process for producing a casting part of a casting mold for melting metal melts, which comprises the preparation of a core sand or molding sand comprising a mold-based material, coated with soluble glass and with a water content in the range of> = about 0.25% by weight to about 0.9% by weight, based on the total weight of the core sand and sand of the mold, filling the core and mold sand into a hollow space that forms the molded part and contacting the core and mold sand with at least one hardening agent before, during and / or after filling and fixing the part molded.
[0030] In general, the use of soluble glass is known in the foundry industry. Soluble glass binders are used for the production of mold and core in series casting. In this case, the hardening can be carried out on a cold tool by reacting with carbon dioxide gas (CO2 gas) or by reacting with an ester. In addition, in recent years, the hardening of mixtures of semi-products bonded with soluble glass through hot tools has been established in a manner similar to the organic hot-box process and the combined hardening by means of heated tools and the absorption of gas, usually with heated air. .
[0031] Sand cores produced in this way are used mainly in the casting of aluminum shell. This is, for example, described in EP 2 163 328 A1.
[0032] The production of the core by means of soluble glass and ester or CO2 gas is classified as odorless and, therefore, compatible with the environment.
[0033] The disadvantages in these processes with soluble glass binders are, in particular, that after casting they disintegrate poorly and that the residual sand is only difficult to regenerate compared to organically bonded sand.
[0034] The objective of the invention is, therefore, in different aspects, to make available a process and a material system for the construction of layered models, which does not present the disadvantages of known processes or at least completely diminishes or overcomes the disadvantages of the state of the art, for example, are compatible with the environment and are economically usable for three-dimensional printing processes.
[0035] The objective is solved by the modalities detailed in the claims.
[0036] In one aspect, the invention refers to a process for building layered models, in which in a construction sector a particulate material is applied in layers and is selectively hardened and these steps are repeated, until a desired model.
[0037] The material here comprises a particulate construction material, which contains a spray dried alkali metal silicate solution. A selective activation of the hardening is carried out, in this case, by means of a solution comprising water and in a drying process.
[0038] By a construction sector, in this case, it is understood, in a very general way, a sector, in which the construction of a model is carried out. According to a preferred embodiment, this could be a construction platform or also a construction container. But this could also be, in addition, any other sector. This also depends, in particular, on the construction process used or the device used. In this way, conveyor belts would also be conceivable or simply just the bottom.
[0039] The application of the material and the selective hardening of the construction material can be carried out, for example, in such a way that initially the particulate material is applied in layers by means of a coating machine and then it is carried out selectively hardening or parts of selective hardening are carried out or some or all of the process steps can be carried out simultaneously.
[0040] The material comprises, according to the invention, a particulate construction material. Such a particulate building material could comprise, in this case, each material known in the prior art for the production of models and, in particular, cores or mixtures thereof.
[0041] As construction material, also mentioned molded semi-product, typical flame resistant materials are suitable, such as, for example, quartz sands, kerfalite, olivine sand and chromite sands. In addition, artificially molded molding materials, such as wax pearls and (Min sand) bauxite sand, are also suitable. Mixtures of different molding materials are also conceivable.
[0042] The building materials, in this case, should not be acidic. In addition, we aim for a grain distribution, which presents its central grain at about half the desired layer thickness. That is, for example, in the case of layer thicknesses of about 300 pm, the median of the particle diameter should measure approximately 150 pm.
[0043] Typical layer thicknesses range from 0.1 mm to 0.5 mm.
[0044] In addition, according to the present invention, the material has a spray dried alkali metal silicate solution. A selective activation of the hardening is carried out by means of a solution comprising water. In addition, a drying process is also carried out.
[0045] Alkali metal silicate solutions, often also mentioned of soluble glass, are known to the person skilled in the art and refer to water-soluble, glassy, solidified potassium silicates and melt (silicic acid salts) with a molar ratio of SiO2 / 1.5: 1 to 4: 1 alkali metal oxide in aqueous solutions.
[0046] Alkali metal silicates, respectively, soluble glass, are produced by smelting quartz sand with sodium carbonate or potassium carbonate at 1400 to 1500 ° C, and the carbon dioxide is released. The solidified melt is brought to the market in a ground state or is immediately converted into a solution of desired concentration. Sodium silicate is conventionally produced by the fusion of silicon dioxide and sodium carbonate in the corresponding molar ratio, as a glassy solidification product, which crystallizes upon being tempered below the melting point.
[0047] Soluble glass, as well as sodium silicate can also be produced by directly dissolving sand in sodium hydroxide solution at high pressure and temperatures up to about 150 ° C.
[0048] The alkali metal silicate solution may also contain other substances. In this way, it can be provided with a surfactant or other auxiliary substances.
[0049] According to the present invention, a spray dried alkali metal silicate solution and also a spray dried one are used. Such preferably presents a calcination loss of 10 - 25% by weight. Spray drying or also spray drying is a process for the production of powders from liquids, in which pulverized liquids are dried with a hot gas.
[0050] The selective hardening according to the present invention, is carried out by means of a solution comprising water. This is presently prescribed, for example, in such a way that a spray-dried soluble glass, respectively, a particulate material that contains a spray-dried alkali metal silicate solution is applied in a layer with a coating machine, such as this. it is known, for example, of rapid prototyping processes known from the prior art and then a solution containing water is applied, for example, by means of a printhead. In this case, the water activates a hardening of the alkali metal silicate solution, so that, after removing the water, for example, through drying, a particulate material is bonded.
[0051] The addition of water leads, in this case, to a dissolution of the powder binder. According to the present invention, a spray dried binder is used. It has the advantage of dissolving more quickly than a normally dried binder. The liquid binder produced selectively in the mold sand mixture through the water-based solvent leads to an adhesion between the particles of the construction material. The water-based solvent, respectively, which contains water, serves to dissolve the alkali metal silicate used as a binder and to contribute to the formation of binder bridges between each of the particle grains (adhesion).
[0052] To activate the solid binder, it must be dissolved, for this, a solvent that contains water is needed. In this case, pure water is the most suitable. However, the water can only be hardly dosed with individual drop producers preferably used for the selective introduction of the solvent. This is due to a relatively low viscosity of approximately 1 mPas, which leads to poor attenuation of the liquid column in the injector. In addition, the surface tension of water is relatively high, so it takes a lot of energy to produce individual drops. Last but not least, water tends to absorb gases, for example, from the air. In the sub-pressures that occur in the droplet producers, the dissolved gas is released and then absorbs the pressure peaks, which must be used for the droplet production. Correspondingly, it is necessary to modify the water for use in droplet producers.
[0053] For this purpose, for example, it can serve a mixture of rheological additives, thickeners, such as glycerin, glycol or layered silicates. In particular, the latter, prove to be advantageous, because in this case, it is a system of purely inorganic material, which behaves neutrally in the foundry, that is, does not lead to pyrolysis.
[0054] The preferable amount of the silicate layer in water is 2 to 20% by weight and even more preferable is the amount of 8 to 12% by weight.
[0055] To the solution that presents water for the selective activation of the hardening, other additives, such as, for example, a dye for the recognition of the mold, a biocide and an agent for the modification of the surface tension, can be added.
[0056] In order to harden the selectively printed material, a drying process is still necessary. Which drying process is most appropriate depends on many factors, such as the material used, the size of the component, the environmental conditions and so on.
[0057] The manufactured component, for example, after construction, can only be dried at room temperature. If this is too slow, then a physical drying process can also speed up the hardening process by removing water at room temperature and / or also increasing the temperature can speed up the hardening process.
[0058] All of this can be done during and / or after the construction process.
[0059] The advantage of the process described according to the invention, is that the unprinted material can be reused.
[0060] The device for the selective application of the hardener does not need to be permanently cleaned, since there is no bonding, as no self-hardening or air-curing substances are used.
[0061] The dry material mixture can be applied with known processes in a simple way in thin layers and a high level of resistance can be obtained.
[0062] The objective of the present invention is also solved by means of a material system for the construction of layered models, being that in a construction sector a material is applied in layers and is selectively hardened and these steps are repeated, until a desired model can be obtained. Here, the material features a particulate construction material and a spray dried alkali metal silicate solution and for the selective activation of the hardening a solution comprising water is used.
[0063] According to a preferred embodiment of the present invention, the particulate material can comprise sand. If, according to a preferred variant, the sand in the particulate material is now used as a building material, then foundry cores can be advantageously produced from the sand.
[0064] Furthermore, it could also be advantageous, if the material comprises an inorganic hardener, in particular, a latent inorganic hardener. The term latent inorganic hardener rewrites, in this case, a substance, which under normal conditions, that is, at room temperature and normal pressure, reacts very slowly with the binder, but at an increase in temperature it leads to rapid hardening. Such a latent hardener could be, according to a particularly preferred embodiment of the present invention, for example, amorphous silicon dioxide.
[0065] If the drying process in a process of the present invention, for example, is thermally induced, then an alkali metal-silica reaction takes place between the alkali metal silicate binder and the amorphous silicon dioxide as a latent hardener.
[0066] If a latent hardener, such as amorphous silicon dioxide, is added, the setting reaction can be reinforced and additionally irreversibly formed. Here, the hardening takes place more quickly and leads to a higher level of resistance if the mixture is added heat.
[0067] According to a preferred embodiment of the present invention, the material has an additional binder. This could be, for example, an adhesive that picks up hydraulically, therefore, an adhesive that needs water to pick up.
[0068] Such binders that pick up hydraulically are, for example, Portland cement, aluminum cement and / or a hydraulic aluminum oxide binder.
[0069] When water is selectively introduced into the material, it may be that the water penetrates the material further than desired and thus leads to inaccuracies in the model to be built. To limit penetration, a hydraulic adhesive, preferably a cement material, can be mixed with the material. Such preferably used cement powders are very fine and have particle sizes preferably less than 30 µm. This leads to a large surface area and, therefore, also a fast and high water absorption. Excess water is thus absorbed by these particles and no longer leads to mold loss. The excess water, which is not used to dissolve the binder, in the hydraulic adhesive is embedded in the cement. Cement thus contributes to increasing strength and makes it possible to act specifically on the compaction curve.
[0070] According to the present invention, the alkali metal silicate solution, respectively, soluble glass, can be contained in the material in all possible forms. In this way, it would be possible, for example, that it is contained in the form of a particle in the material. The soluble glass particles should, in this case, be as small as possible, to ensure high solubility.
[0071] Conventional particle diameters for this purpose are less than 150 pm and even more advantageously, less than 100 pm.
[0072] Typical representatives of spray-dried soluble glass powders are, for example, Sikalon A from Woellener or Pirtil A from Cognis. These are produced through spray drying of aqueous alkali metal silicate solutions (sodium or potassium silicate solutions). For the description of the process, reference can also be made in this case to Ullmanns Enzyklopãdie der technischen Chemie 1982, 4th edition, volume 21, page 412.
[0073] As another variant it would also be possible, that the particulate construction material, respectively, the semi-product is coated with the spray dried alkali metal silicate solution or the alkali metal silicate solution is applied over it. Such a process represents the so-called coaten, in which the coated semi-product is can be prepared, for example, by spray drying an aqueous mixture of the semi-product and the alkali metal silicate binder. Then, the coated semi-product is applied in layers and printed to an aqueous solution.
[0074] Preferably, in a process according to the invention, respectively, material system, the soluble glass should have a molar ratio M2O: SiO2 of 1.6 to 3.8, in particular, of 1.9 to 3, 4 (M = alkali metal, sodium and / or potassium).
[0075] Conventionally, a spray dried alkali metal silicate binder, respectively, an alkali metal silicate solution has a calcination loss of 10 40% by weight, preferably 15-25% by weight.
[0076] According to a particularly preferred embodiment of the present invention, the latent hardener comes from the group of silicic acid materials that can carry out an alkali metal-silicic acid reaction. Particularly preferably, in this case, thermal or pyrogenic silicic acids are used, which result, for example, as a by-product in the production of crude or ferrous silicon, fumed microsilica or condensed fumed silica.
[0077] Advantageously, the latent hardener is selected from the group of synthetic silicic acids, in particular, thermal and / or pyrogenic silicic acids. The term synthetic silicic acid refers here to artificially produced silicic acids, such as thermally produced silicic acids through flame pyrolysis, in the electrofusion furnace or plasma, as well as to precipitation silicic acids.
[0078] By "synthesis" is understood the natural or artificial production, optionally in multistages and mainly, specific, of chemical compounds of the elements, through the construction of simpler compounds or through the degradation of more complex structures.
[0079] A reaction according to the present invention can proceed, for example, in this way. The spray-dried binder is activated by adding water, then reacts with a latent hardener preferably added, for example, amorphous silicon dioxide. The hardening reaction that takes place, in this case, an alkali metal-silicic acid reaction, is accelerated through energy supply, in particular heat, and then leads to a faster hardening of the resulting model and greater resistance model than without the addition of latent hardener.
[0080] Also the storage stability of cores with high air humidity, as well as thermal stability, for example, the flexing of cores, in the casting process, increases markedly in comparison to the cores prepared only by means of silicate binders alkali metals as binders.
[0081] According to a particularly preferred embodiment of the present invention, the fraction of alkali metal silicate, therefore, the fraction of binder added to the material, in particular particulate material, such as, for example, sand, which is present in solid form before dissolving with the printing solution, it matters 2-18, preferably 3-10% by weight.
[0082] Advantageously, the fraction of the latent hardener in relation to the binder present in solid form, matters in 5-90% by weight.
[0083] If the material, according to a preferred modality, also presents flame resistant materials and / or loading materials, then the properties of the model produced, such as the foundry core, can be optimized.
[0084] Such flame resistant materials and / or filler materials are used, for example, also as coatings for semi-products, for example, graphite, aluminum oxide, zirconium silicate, to increase the quality of the foundry. Other additives to sand can be water-soluble binders, phosphates or carbohydrates, such as, for example, dextrin.
[0085] According to a preferred embodiment of the present invention, the material comprises a mixture of spray dried alkali metal silicate binder, sand, amorphous silicon dioxide in a proportion of 1.5-15% by weight: 80-98: 0.2-8.
[0086] Advantageously, the solution to activate the selective hardening has a layer silicate, preferably containing 5-15% by weight.
[0087] Preferably, the solution to activate 17/19 selective hardening is applied with an inkjet printhead, preferably with piezo technology.
[0088] In order for the hardening in the process to be accelerated, the heat supply could also be advantageously provided.
[0089] This feeding can be carried out, for example, through convection and / or heat radiation.
[0090] The solid bodies produced in this way preferably have a flexural strength at three points approximately greater than 200 N / cm2.
[0091] The invention is illustrated below, based on preferred embodiments in the following examples. Example:
[0092] A material system for use for a three-dimensional printing process is prepared, for example, as follows:
[0093] 90% by weight of quartz sand of the GS 14 RP types with an average grain diameter of 0.13 mm from the company Grube Strobel are intensively mixed with 6% by weight of soluble glass powder (for example, molar module 2.10, Portil A by Cognis), 2% by weight of synthetic silicon dioxide from the arc furnace (Microsilica 971 U by Elkem) as a latent hardener, as well as 2% by weight of cement alumina (CA 14 S from Almatis) as a hydraulic binder, so that the mixture is completely homogeneous.
[0094] This dry semi-product mixture is applied in layers in a construction sector. The water is then selectively compressed with a conventionally finished printhead for three-dimensional printing processes using inkjet printing technology, so that the soluble glass binder is activated. In the printed places, the binder dissolves and glues the surrounding particles.
[0095] Selective printing occurs, in this case, preferably according to computer data, to produce a desired model.
[0096] In this case, the part or parts of the particulate material can be heated before selective printing. In this way, the drying process to harden can be carried out more quickly.
[0097] Now, a semi-product mix layer is applied again and then, selectively printed again according to computer data.
[0098] This process is repeated so many times, until the desired model is built. The desired body is formed, which after the completion of the layered construction process must be released from the surrounding sand.
[0099] To increase the strength and, at the same time, to flatten the surface, the finished components can be sprayed with a soluble glass solution or with a water-soluble glass mixture and then dried in the oven.
[00100] Mixed unprinted sand can be infiltrated again in the process. For this, it must be removed from the respective models, molded and sieved parts, to avoid thicker impurities. Advantageously, the reused semi-product is mixed with fresh material before a new use, in order to obtain a constant quality. The addition of new sand should preferably be between 10 and 50% by weight.
[00101] It has been demonstrated that a good adhesive effect can be obtained when 2 and 12% by weight of binder mixture (mixture of spray dried soluble glass and amorphous silicon dioxide) are mixed in the sand.
[00102] Advantageously, the addition matters between 3% and 6%. The resistances obtainable are then found when using quartz sand of the GS14 types (MK: 0.13 mm / AFS 97 index) at about 280 N / cm2. To obtain sufficient activation of the binder, between 3% and 18% must then be dosed based on the weight of the aqueous solution for the semi-product. Advantageously, the amount to be dosed is between 5% and 10%.
[00103] In order to prevent water from unintentionally penetrating into the unprinted marginal areas and there also leading to a catching reaction and, with this, it can lead to a worsening of the image fidelity and dissolution, a prediction can be predicted accelerated pick-up reaction.
[00104] This is achieved, for example, through the introduction of heat. An increase in the sand temperature from 20 ° C to 60 ° C speeds up the setting process from several to a few hours. With a further increase to 90 ° C, the handle can be carried out, even, in a few minutes. By introducing heat, the hardening reaction of the binder with the latent hardener, amorphous silicon dioxide, is markedly accelerated. However, in this case, it must be noted that the processed layers cannot connect separately from each other, because otherwise the layers do not connect. That is, depending on the size of the construction field and the speed of the process, the duration of the pick should not be less than 10 minutes.

权利要求:
Claims (12)
[0001]
1. Process for building layered models, where a particulate material is applied in layers in a construction area by means of a coater, and is then cured selectively, and these steps are repeated until a desired model is obtained, said particulate material comprising a particulate construction material, said process being characterized said particulate material comprises a spray dried alkaline silicate solution, selective curing activation being carried out by means of a solution containing water, and a drying process is performed.
[0002]
2. Process according to claim 1, characterized by the fact that the particulate material comprises sand.
[0003]
3. Process according to claim 1 or 2, characterized by the fact that the particulate material comprises an inorganic curing agent.
[0004]
Process according to any one of claims 1 to 3, characterized in that the particulate material comprises an additional binder.
[0005]
Process according to any one of claims 1 to 4, characterized in that the spray dried alkaline silicate solution is contained in the form of particles in the particulate material.
[0006]
Process according to any one of claims 1 to 5, characterized in that the particulate material comprises a latent curing agent selected from the group consisting of synthetic silica.
[0007]
Process according to any one of claims 1 to 6, characterized in that the spray dried alkaline silicate is present in an amount of 2-18% by weight of the particulate material.
[0008]
Process according to any one of claims 3 to 7, characterized in that the latent curing agent is present in an amount of 5-90% by weight of the alkaline silicate.
[0009]
Process according to any one of claims 1 to 8, characterized in that the particulate material further comprises refractory materials and / or filler materials.
[0010]
Process according to any one of claims 1 to 9, characterized in that the particulate material comprises a mixture of spray dried alkaline silicate binder, sand, amorphous silicon dioxide, at a weight% ratio of 1 , 5-15: 80-98: 0.2-8.
[0011]
11. Process according to any one of claims 1 to 10, characterized in that the solution to activate the selective curing includes a silicate sheet.
[0012]
12. Process according to any one of claims 1 to 11, characterized in that the solution for selective curing is applied by an inkjet print head, or / and that the curing is accelerated by heat.

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TWI378130B|2012-12-01|

同族专利:

公开号 | 公开日

US9358701B2|2016-06-07|

MX2013014663A|2014-12-05|

EP2723697A1|2014-04-30|

KR102010334B1|2019-10-21|

ES2683954T3|2018-09-28|

KR20140078584A|2014-06-25|

DE102011105688A1|2012-12-27|

JP5946526B2|2016-07-06|

CN103702958B|2016-05-04|

US20140212677A1|2014-07-31|

BR112013032506A2|2017-02-21|

CN103702958A|2014-04-02|

JP2014516845A|2014-07-17|

WO2012175072A1|2012-12-27|

EP2723697B1|2018-05-16|

MX358187B|2018-08-08|

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