EP3297810A1 - Procédé à base de résine phénolique - Google Patents

Procédé à base de résine phénolique

Info

Publication number
EP3297810A1
EP3297810A1 EP16730241.3A EP16730241A EP3297810A1 EP 3297810 A1 EP3297810 A1 EP 3297810A1 EP 16730241 A EP16730241 A EP 16730241A EP 3297810 A1 EP3297810 A1 EP 3297810A1
Authority
EP
European Patent Office
Prior art keywords
binder
temperature
component
particulate material
solvent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP16730241.3A
Other languages
German (de)
English (en)
Inventor
Daniel GÜNTHER
Florian MÖGELE
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Voxeljet AG
Original Assignee
Voxeljet AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Voxeljet AG filed Critical Voxeljet AG
Publication of EP3297810A1 publication Critical patent/EP3297810A1/fr
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/165—Processes of additive manufacturing using a combination of solid and fluid materials, e.g. a powder selectively bound by a liquid binder, catalyst, inhibitor or energy absorber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/141—Processes of additive manufacturing using only solid materials
    • B29C64/153—Processes of additive manufacturing using only solid materials using layers of powder being selectively joined, e.g. by selective laser sintering or melting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/188—Processes of additive manufacturing involving additional operations performed on the added layers, e.g. smoothing, grinding or thickness control
    • B29C64/194—Processes of additive manufacturing involving additional operations performed on the added layers, e.g. smoothing, grinding or thickness control during lay-up
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/20—Apparatus for additive manufacturing; Details thereof or accessories therefor
    • B29C64/245—Platforms or substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/20—Apparatus for additive manufacturing; Details thereof or accessories therefor
    • B29C64/295—Heating elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/30—Auxiliary operations or equipment
    • B29C64/386—Data acquisition or data processing for additive manufacturing
    • B29C64/393—Data acquisition or data processing for additive manufacturing for controlling or regulating additive manufacturing processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/40—Structures for supporting 3D objects during manufacture and intended to be sacrificed after completion thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
    • B29C67/24—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
    • B33Y40/20—Post-treatment, e.g. curing, coating or polishing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y50/00—Data acquisition or data processing for additive manufacturing
    • B33Y50/02—Data acquisition or data processing for additive manufacturing for controlling or regulating additive manufacturing processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K2103/00—Materials to be soldered, welded or cut
    • B23K2103/30—Organic material
    • B23K2103/36—Wood or similar materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K2103/00—Materials to be soldered, welded or cut
    • B23K2103/30—Organic material
    • B23K2103/42—Plastics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/04—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould using liquids, gas or steam
    • B29C35/041—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould using liquids, gas or steam using liquids
    • B29C2035/042—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould using liquids, gas or steam using liquids other than water
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2086/00—Use of specific polymers obtained by polycondensation or polyaddition, not provided for in a single one of main groups B29K2059/00 - B29K2085/00, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/25—Solid
    • B29K2105/251—Particles, powder or granules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2509/00—Use of inorganic materials not provided for in groups B29K2503/00 - B29K2507/00, as filler
    • B29K2509/02—Ceramics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/007—Hardness
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Definitions

  • the invention relates to a method and a device for producing three-dimensional components. These moldings are suitable for use in foundry applications, especially as molds and cores.
  • European Patent EP 0 431 924 B1 describes a method for producing three-dimensional objects from computer data.
  • a particulate material is applied in a thin layer on a platform and this selectively printed by means of a print head with a binder material.
  • the particle area printed with the binder sticks and solidifies under the influence of the binder and optionally an additional hardener.
  • the printed and solidified areas create a three-dimensional object (component).
  • This object made of solidified particulate material is embedded after its completion in loose particulate material and is subsequently freed from it. This is done for example by means of a nipple.
  • the desired objects then remain, which are then removed from the residual powder, e.g. be freed by brushing.
  • the further process conditions can be problematic and suboptimal for the production of advantageous components.
  • a particulate material is applied layer by layer with a layer thickness on a building area in a space, selectively a binder is applied, the temperature in the space and / or in the applied Parti kelmateriai to a desired temperature is set and the steps of material application and binder application are repeated until a desired component is obtained, wherein the temperature in the installation space and / or in the applied material is set to at least 70 ° C and maintained for at least 2 hours, wherein the areas to which selective binder has been applied solidify and form the component.
  • an unproblematic binder system can be used, which is based on water or alcohol as solvent, and set in the applied particulate material over a longer period of time, a temperature of at least 70 ° C and maintained. It is advantageous that with the method a very large area in the applied particulate material thus maintains a homogeneous desired temperature and thus a uniform solidification and advantageous component properties can be obtained. This not only has the advantage that homogeneous material properties are achieved in the component, but also that a large area of the installation space for the production of components can advantageously be used and the unused edge area of the installation space provided with particulate material remains relatively small. This increases the efficiency of the device and thus reduces the cost per component or volume component.
  • the binder system used in the process is preferably poorly reactive at room temperature and the machine parts, and particularly the printhead, can be easily cleaned and thus maintained without significant problems.
  • Figure 1 Schematic representation of the components of a
  • FIG. 2 Sequence of a conventional 3D printing process with the use of a layer-wise radiation curing.
  • FIG. 3 Sequence of a building process with radiation hardening which does not take place in every layer.
  • Fig. 4 Schematic representation of the application of binder (400) on the submitted particulate material, wherein (401) represents a particle and the dark arrow represents the penetration direction. This results in the strength of the component by the binder connects the particles of the particulate material and it comes to a curing of the binder and thus a firm connection of the binder with the particulate material.
  • Figures 4a-4d describe the sequence of binder penetration into the
  • Fig. 5 In Fig. 5a and 5b, the energy input / heat input (500, 501, 502) and the energy loss / heat loss (503, 504, 505) are shown.
  • Fig. 5c a highly inhomogeneous temperature distribution is shown and in this case, the isotherms (510-514) within which certainly a solidification reaction occurs far in the center of the building container. As a result, the usable space is reduced considerably and the economy of the device and the method are disadvantageous.
  • Fig. 5c the situation is shown in the disclosed method and it is clear that the usable space or the usable applied powder cake is much larger and thus an increased efficiency of the machine is accompanied and at the same time the component properties can be beneficial.
  • This is shown by the isotherm line 510 which includes a large area that is kept homogeneous in temperature during the process and thus has positive process results.
  • Fig. 6 Production of the prepolymer using the example of a resol
  • 3D printing processes are all processes known in the prior art which enable the construction of components in three-dimensional shapes and are compatible with the described process components and apparatuses aqueous solutions and / or other fluid components or solvents which must be removed from the molded part or which escape from the molded part to be produced or during its solidification.
  • the solidification and the quality of the molded part can be influenced by the invention in a targeted manner, other quality characteristics being equal stay or even be positively influenced.
  • “Shaped body”, “model”, “3D molded part” or “component” in the context of the invention are all three-dimensional objects produced by the method according to the invention and / or the device according to the invention, which have a dimensional stability.
  • any known 3D printing apparatus may be used which includes the required components continuous procedures and others Professional known components, which are therefore not detailed here.
  • a "construction platform” or “construction area” moves relative to the printing and coater plane, which moves during the construction process in interrupted movements in layer thickness, which defines the layer thickness move the remaining parts of the device nacho ben and thus the layer thickness or layer thickness is set.
  • a "construction container” or “job box” realizes a construction space. He therefore has a floor, walls and an open access area, the building level, on.
  • the build container always has parts that do not move relative to the frame of the 3D printing device.
  • Interchangeable construction containers, so-called swap bodies enable the machine to be operated almost constantly, since the swap bodies can be moved in and out of the machine. The parts of a first construction process can thus be unpacked outside the device (SD printing device), while new parts can already be printed within the machine in a second construction container.
  • Construction space in the sense of the invention is the geometrical location in which the particle material bed grows during the construction process by repeated coating with particulate material.Furthermore, the installation space is limited by a floor, the building platform, by walls and an open cover area, the building level Construction level can be horizontal, but for example in continuous processes also form an angle, so that the layer order is oblique at an angle.
  • particulate materials or as “building materials” or “particulate material” all known for powder-based 3D printing materials may be used, in particular sands, ceramic powder, metal powder, plastics, wood particles, fiber materials, celluloses and / or lactose powder.
  • the particulate material is preferably a dry, free-flowing powder, but a cohesive, cut-resistant powder may also be used.
  • the particulate material used may be understood as a "passive powder material” because it is in the binding reaction, i. the solidification of the component is not directly involved, but only solidified by the binder system to a solid component or "connected” is. It can behave inertly.
  • the applied particulate material may also be referred to as a powder cake.
  • “Setting the temperature” or “tempering” means that a specific temperature is set in the installation space or / and the applied particulate material or that the installation space is set to a selected temperature.
  • the applied particulate material is tempered and the temperature is maintained , eg to about 60, 70, 80, 90, 100, 110, 120, 130, 140, 150 ° C, or 80 to 100 ° C.
  • a “binder” or “binder system” is the material that is selectively applied to the particle material by means of a printhead, which leads to solidification and thus to the production of the component includes a solvent and other components, eg monomers, oligomers and / or polymers.
  • the binding mechanism is a polymerization reaction. The result is a solid material that is able to bind the particles in the powder.
  • a prepolymeric phenolic resin is preferred.
  • “Diffusion length” corresponds to the spreading of an applied binder in the particulate material and is influenced inter alia by the volume, the temperature, its composition.
  • a method for the layered construction of components wherein a particulate material with a layer thickness is applied to a construction area in a construction space selectively, a binder is applied, the temperature in the installation space and / or in the applied particulate material to a desired temperature is set and the steps of material application and binder application are repeated until a desired component is obtained, wherein the temperature in the installation space and / or in the applied material is set to at least 70 ° C and maintained for at least 2 hours, wherein the areas on which selective binder has been applied, solidify and form the component.
  • the disclosed method makes it possible to increase the effective space within the applied powder cake, since a constant and overflow the required temperature for the reaction period can be set and maintained.
  • the temperature is chosen so that the reaction temperature required for solidification with positive component properties in the powder cake is set to be homogeneous.
  • the temperature is set at 70 to 90 ° C, preferably at least 80 ° C, more preferably at least 90 ° C, even more preferably 80 to 150 ° C, even more preferably 80 to 100 ° C.
  • This is also called isotherm, and is preferably an isotherm of 80 ° C, preferably of 90 ° C.
  • the temperature is maintained for a period of time required for the reaction, preferably for 3 to 10 hours, more preferably for 4 to 6 hours, and even more preferably for at least 4 hours.
  • the particulate material is a plastic, a sand, a ceramic or a metal.
  • the particle size can be selected as required in conjunction with the other process parameters.
  • the mean grain size is at least 8 ⁇ , more preferably 10 ⁇ to 1 mm.
  • the particle material can be grown in different layer thicknesses, preferably the layer thickness is 50 to 800 ⁇ .
  • the binder is tuned to the other process materials and conditions, and it is preferable to use as the binder a binder system comprising monomers, oligomers or / and polymers and a solvent, preferably the solvent is an aqueous or alcohol-containing solvent.
  • the component obtained by the method preferably has a green strength in the component of at least 280 N / cm 2.
  • a final strength (bending strength) in the component of at least 300, preferably at least 500 N / cm 2 can be achieved directly or after further process steps.
  • the process conditions are adjusted so that the manufactured component has a loss on ignition of less than 3%, preferably less than 2.5%, more preferably less than 2.2%.
  • the disclosure relates to a binder system comprising monomers, oligomers or / and polymers and a solvent, preferably, the solvent is an aqueous or alcohol-containing solvent.
  • the binder system comprises a prepolymeric phenolic resin.
  • the disclosure relates to a material system comprising a particulate material as described above and a binder system as described above.
  • the disclosure relates to a device for producing a component, comprising a construction space with a construction platform, means for applying a particulate material, means for selectively applying a binder system, means for adjusting a temperature in the installation space and / or the particulate material.
  • a device for producing a component comprising a construction space with a construction platform, means for applying a particulate material, means for selectively applying a binder system, means for adjusting a temperature in the installation space and / or the particulate material.
  • the disclosure relates to a solid (component) produced by a method, a binder system, by means of a material system and / or a device as described herein, wherein the solid preferably has a flexural strength of 500 N / cm 2.
  • One aspect of the process is a binder system or binder (400) which is printed on a reaction neutral powder (401) and cures at substantially elevated temperature for several hours. This curing takes place to a large extent during the construction process. The whole, resulting powder cake is kept warm for hours.
  • various particulate materials (401) can be used. These can be ceramic powder, sand or metal powder.
  • the powder grains (401) should not be significantly less than 10pm for the process. Larger particles (401) than 1mm generally make reliable processing difficult. These statements refer to the mean grain size. Significant proportions of said maximum and minimum grains (401) are detrimental to the process even if the mid grain requirements are met.
  • the particles are processed in the device by a coater (101) in conjunction with the building platform (102) to form a thin layer (107).
  • the particulate material (401) is presented at or from a starting position and smoothed by crossing the coater (101) over the construction field.
  • the respective bearings of the construction platform determines the layer thickness.
  • the powder cake is kept at a temperature of 80 ° C for at least 4 hours. This results in a bending strength of more than 300 N / cm 2 in the components with an ignition loss of less than 2.2%.
  • the binder system (400) contains as binders monomers, oligomers and / or polymers. These are dissolved in a solvent.
  • the binding mechanism is a polymerization reaction. The result is a solid material that is able to bind the particles in the powder.
  • As the base material a prepolymeric phenolic resin is preferred.
  • the binder system (400) according to the invention is designed for use in ink jet jerk heads (100) with piezo elements.
  • the viscosity is in a range of 5-20 mPas.
  • the vapor pressure less than 3000 Pa at room temperature.
  • the surface tension in the range of 30-50 mN / m.
  • the binder system is set so that a reversible drying of the printhead only after about 1 minute prevents the first nozzle on the function.
  • the binder system (400) is extremely weak at room temperature in its reactivity. Therefore, the printhead (100) is protected and the printhead works with high reliability even after a long life. Dried binder can still be easily removed even after weeks at room temperature. This facilitates both the cleaning of the device and the re-commissioning of dried nozzles.
  • the solvent for the binder system may be water in the case of phenolic resins.
  • the binder system is classified with appropriate handling as little harmful to health.
  • the print head (100) is actively or passively cooled due to heating by the hot construction field surface, so that the drop mass and thus the entry can be kept constant throughout the construction process.
  • the passive cooling can be done by contacting with the print head cleaning.
  • An active cooling for example, by a cooling element, with Cooling water is flowed through and attached to the print head (100) can be achieved. Introducing pre-cooled compressed air and a fan are suitable as a cooling device.
  • the printed on the print head (100) binder penetrates when hitting the surface of the particulate material, depending on the surface tension, slowly into the powder cake. In this case, a certain diffusion length is desired. This diffusion is necessary to connect the individual layers together. This diffusion length depends on the liquid parameters, but also on the temperature on the construction field. In addition, the temperature control during construction is chosen so that the printed layers slowly harden and thus allow a composite layer.
  • the apparatus has means (200, 300-304) for heating and keeping warm the powder cake.
  • the introduced energy can be isolated in part by the powder, so that once warmed up powder can not cool down quickly.
  • infrared heat sources can be used. These may be static over the construction field (302) or moved with moving parts of the device over the construction field (200).
  • Halogen spotlights made of quartz glass as well as ceramic spotlights are suitable.
  • Mirrors for IR radiation are also suitable for influencing and controlling the heat balance.
  • an IR emitter with a maximum power of 9.5kW and one meter in length can be used to heat a construction field of 100x60cm.
  • the radiator is, for example, back and forth over the construction field at a speed of 0.05 m / s.
  • This process is usually combined with the coating process. With a coating time of about 60 seconds, which essentially comes about through the printing and the exposure, over 90 ° C can be achieved in the powder cake during the construction process.
  • a separate exposure run every n layers x times in addition to the exposure described and / or as the sole heating routine can be used with n> 2, preferably every 2 to 5 layers, particularly preferably all 3 layers and exposed x> 1 times, preferably 2 to 5, more preferably 3 to 4 times.
  • hot air can sweep over the site (301) and heat it up.
  • hot air blowers (301) suitable.
  • a direct preheating of the powder with an air flow or a resistance heating is also possible.
  • a contacting heated metal may be passed over the powder (304) to heat it.
  • Another suitable process means are heaters in the building container wall (300) and / or in the building platform (301). These can bring heat to the process. On the other hand, these can reduce heat losses as active insulation.
  • Such heaters can be designed, for example, as electrical resistance heaters. These can be regulated via standard controllers. Here, e.g. Foils commonly used on metallic surfaces, such as the building container walls, can be glued. Equally effective heating cartridges are inserted into holes in metal plates.
  • the active isolation can be carried out with a heat transfer medium.
  • the heat transfer medium such as, for example, water or oil in pipes, which usually consist of copper, which in turn run contacting within the Jobboxwand and the Jobbox asks and preferably meandered to achieve the most uniform heating of the box.
  • Passive insulation is also helpful for the temperature control in the construction container.
  • This can be different "materials” like them Also used in the construction industry are: mineral insulation, plastics, foams but also air, vacuum, etc.
  • the passive insulation is installed so that the heat flow is reduced from the construction container.
  • the controller specifies the temperature control within the device. For this purpose, means for detecting important temperature variables may be present in the device. This allows control circuits to be realized.
  • a simple variant is control of the power that is introduced into the device. During the warm-up phase of the machine, a higher power is introduced. During the ongoing production process, performance is gradually reduced.
  • heating elements and insulation must be tuned so that a homogeneous temperature field (e.g., Figure 5d) is established in the powder cake.
  • a homogeneous temperature field e.g., Figure 5d
  • the required homogeneity depends on the binding system. In this case, a certain threshold must be safely exceeded, so that a secure hardening of the binder is guaranteed.
  • the temperature should not be too high, otherwise the printing and building process will be disturbed. This should be 90 ° C Construction surface temperature should not be exceeded. To achieve sufficient strength, 80 ° C must be exceeded. Thus, the temperature must be within a range of 10K.
  • the binder system is a thermosetting resole resin and / or novolac prepolymer which, under the conditions already described, partially or completely reacts during the building process to form an insoluble and non-fusible resit.
  • the temperature control during the entire construction process is chosen so that the curing does not take place adhoc, but runs over a period of several hours and allows the composite layer. (Figure 7)
  • Resoles and novolaks are prepolymers of a phenol-formaldehyde cocondensate. Resoles are prepolymers which are polymerized with phenol with an excess of formaldehyde under alkaline conditions. ( Figure 6)
  • Resoles have an increased number of free hydroxyl groups which tend to condensation under the influence of temperature and form an insoluble Resit.
  • Novolaks are prepolymers, which were synthesized under excess of formaldehyde under acidic conditions and co-condensed with resole under the influence of temperature to the Resit or polymerized by addition of a formaldehyde donor (eg urotropin) and temperature increase.
  • a formaldehyde donor eg urotropin
  • the prepolymer contains residual monomers of phenol and formaldehyde.
  • the content of phenol is preferably below 5% and particularly preferably below 1%.
  • the formaldehyde content is preferably below 0.3%, more preferably below 0.1%.
  • the binder is diluted by adding a solvent consisting of one and / or multiple alcohols and / or water or exclusively water, to the extent that the viscosity in the range of 5-20 mPas, preferably 5-10 mPas and more preferably between 5-8 mPas.
  • modifiers such as polyhydric alcohols such as glycol, propanediol or propylene glycols, furthermore carboxymethylcelluloses, xylitol, sorbitol or gum arabic. Preference is given to 1% -9%, more preferably 3% to 7%.
  • the binder fluid is composed of 30% -40% of the prepolymer, 60% -70% solvent, and 1% -7% viscosity modifier.
  • the binder entry can be adjusted over a wide range depending on the desired final strength and loss on ignition. Usually, the entry and the temperature control is selected so that the green strength does not fall below 280 N / cm 2 in order to ensure safe handling of the components. If the condensation reaction is not fully achieved during the construction process, a downstream furnace process can complete the reaction.
  • the components are preferably postbaked at 120 ° C.-150 ° C. for 1-4 h, more preferably at 130 ° C.-140 ° C. for 2-3 h. Still residual solvent is also completely expelled in this process.
  • entries of 5% -8% based on the weight of particulate matter are used, which provide sufficient green strength as well as high ultimate strength.
  • Binder mixture resole / novolak prepolymer 35%, water / i-propanol (80/20) 63%, 1,2-propanediol 3%

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Optics & Photonics (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Ceramic Engineering (AREA)
  • Civil Engineering (AREA)
  • Composite Materials (AREA)
  • Structural Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Producing Shaped Articles From Materials (AREA)

Abstract

L'invention concerne un procédé, un dispositif, un système de liant (400) et un système de matériau pour la fabrication de pièces (103) selon une technique de structure stratifiée, la température régnant dans l'espace de montage et/ou dans le matériau appliqué étant réglée à au 70 °C minimum et maintenue pendant 2 heures minimum, les zones dans lesquelles les liants (400) ont été appliqués de manière sélective, se solidifiant et formant la pièce (103).
EP16730241.3A 2015-05-20 2016-05-18 Procédé à base de résine phénolique Pending EP3297810A1 (fr)

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DE102015006363.4A DE102015006363A1 (de) 2015-05-20 2015-05-20 Phenolharzverfahren
PCT/DE2016/000209 WO2016184448A1 (fr) 2015-05-20 2016-05-18 Procédé à base de résine phénolique

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DE102015006363A1 (de) 2016-12-15
US20210016500A1 (en) 2021-01-21
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KR20180011153A (ko) 2018-01-31
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