EP4051652A1 - Procédé d'impression 3d et moulage produit par ce procédé à l'aide de lignosulfonate - Google Patents

Procédé d'impression 3d et moulage produit par ce procédé à l'aide de lignosulfonate

Info

Publication number
EP4051652A1
EP4051652A1 EP20816382.4A EP20816382A EP4051652A1 EP 4051652 A1 EP4051652 A1 EP 4051652A1 EP 20816382 A EP20816382 A EP 20816382A EP 4051652 A1 EP4051652 A1 EP 4051652A1
Authority
EP
European Patent Office
Prior art keywords
printing
molded part
powder
printing process
mpas
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
EP20816382.4A
Other languages
German (de)
English (en)
Inventor
Ingo Gnüchtel
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 GmbH
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 EP4051652A1 publication Critical patent/EP4051652A1/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
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/10—Formation of a green body
    • B22F10/14—Formation of a green body by jetting of binder onto a bed of metal powder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/60—Treatment of workpieces or articles after build-up
    • B22F10/68—Cleaning or washing
    • 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
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/38—Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process
    • B29C33/3807—Resin-bonded materials, e.g. inorganic particles
    • 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
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/38—Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process
    • B29C33/3814—Porous moulds
    • 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
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/38—Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process
    • B29C33/3842—Manufacturing moulds, e.g. shaping the mould surface by machining
    • 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
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/44—Moulds or cores; Details thereof or accessories therefor with means for, or specially constructed to facilitate, the removal of articles, e.g. of undercut articles
    • B29C33/52—Moulds or cores; Details thereof or accessories therefor with means for, or specially constructed to facilitate, the removal of articles, e.g. of undercut articles soluble or fusible
    • 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
    • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
    • B29C39/22—Component parts, details or accessories; Auxiliary operations
    • B29C39/26—Moulds or cores
    • 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
    • B29C64/264—Arrangements for irradiation
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C04B26/28—Polysaccharides or derivatives 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
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/30—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core
    • 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
    • B29K2001/00—Use of cellulose, modified cellulose or cellulose derivatives, e.g. viscose, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—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
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—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
    • B33Y30/00—Apparatus for additive manufacturing; Details thereof or accessories therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—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
    • 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 [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00034—Physico-chemical characteristics of the mixtures
    • C04B2111/00181—Mixtures specially adapted for three-dimensional printing (3DP), stereo-lithography or prototyping
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/10—Mortars, concrete or artificial stone characterised by specific physical values for the viscosity
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
    • C04B2201/52—High compression strength concretes, i.e. with a compression strength higher than about 55 N/mm2, e.g. reactive powder concrete [RPC]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

  • the present invention relates to a material system for 3D printing, to a 3D printing process using a lignin-containing component or derivatives thereof, to soluble molded parts that are produced by means of powder-based layer construction and the use of the molded parts.
  • the European patent EP 0 431 924 B1 describes a method for producing three-dimensional objects from computer data.
  • a particle material is applied in a thin layer to a platform and a liquid is selectively printed on this using a print head.
  • the particles combine and the area solidifies under the influence of the liquid and possibly an additional hardener.
  • the platform is then lowered by a layer thickness in a building cylinder and provided with a new layer of particulate material, which is also printed as described above. These steps are repeated until a certain, desired height of the object is reached.
  • a three-dimensional object is created from the printed and solidified areas. This process can be used to process various particle materials, including - but not exhaustively - natural biological raw materials, polymer plastics, metals, ceramics and sands.
  • Sand particles for example, can be processed with binder systems using powder-based 3-D printing. This includes, among other things, the cold resin bond, which is used in foundries as well as in 3D printing.
  • Inorganic binders are also used in this field. In the foundry industry, these are the environmentally friendly alternative to cold resin binders.
  • the invention relates to a material system which comprises a particulate material or a mixture and a pressure fluid.
  • the invention relates to a method for producing molded parts which can be used as a lamination mold or a cold casting mold and which, if necessary, can be easily removed by washing with an aqueous solution or liquid.
  • FIG. 1 Representation of a simple printed molding as a lamination mold for a laminate.
  • FIG. 2 Washing out of the laminate with destruction of the printed part.
  • FIG. 3 Cored laminate.
  • FIG. 4 Finished laminate
  • FIG. 5 Process sequence for cold casting with subsequent washing out of the mold
  • a solution to the problem underlying the invention in cold casting as well as in the production of laminates is a material system and / or a method for producing 3D printed molded bodies, a lignin or derivatives thereof being contained in the printing fluid, which is preferably done with the aid of a solvent such as water can be demolded with destruction.
  • a solution is provided by a material system suitable for a 3-D printing process or a 3-D printing process material system comprising or consisting of a particulate material and a printing liquid, the particulate material being selected from the group consisting of inorganic particulate materials such as quartz sand, olivine sand, kerphalite, Cerabeads, ceramics, metal powder or other organic particle materials such as wood powder, starch powder or cellulose powder, the particle material is preferably untreated, the printing fluid comprising or consisting of a liquid selected from the group consisting of water or an aqueous solution and a lignin-containing component or derivatives thereof, preferably lignosulfonate.
  • the particulate material being selected from the group consisting of inorganic particulate materials such as quartz sand, olivine sand, kerphalite, Cerabeads, ceramics, metal powder or other organic particle materials such as wood powder, starch powder or cellulose powder, the particle material is preferably untreated
  • a material system according to the invention offers, inter alia, the advantage that it is inexpensive, since either inexpensive insoluble materials can be used and / and the insoluble particulate material can essentially be reused. This is particularly advantageous with expensive particulate materials.
  • lignin is a renewable raw material that is easily available and also inexpensive.
  • the printing fluid is easy to use, environmentally friendly and protects the print head and its components, which represent a significant cost factor in 3D printing machines and their processes.
  • the printing fluid can additionally contain or comprise a component selected from the group consisting of water-soluble plastics such as polyvinylpyrolidone, polyethylene glycol, polyvinyl alcohol or polyacrylic acid or other known water-soluble components that are compatible with the other material components.
  • water-soluble plastics such as polyvinylpyrolidone, polyethylene glycol, polyvinyl alcohol or polyacrylic acid or other known water-soluble components that are compatible with the other material components.
  • the individual components are set in their relationship to one another in such a way that a 3D printing process can advantageously be carried out and leads to the desired properties of the molded parts produced.
  • the pressure fluid is set and adapted equally to the other material components, wherein the pressure fluid can consist of or comprise polar organic and / or inorganic liquids, preferably water and / or alcohols.
  • the material system according to the invention is characterized in that the pressure fluid consists of or comprises polar organic and / or inorganic fluids, preferably water and / or alcohols.
  • the material system can preferably be characterized in that it additionally contains a soluble starch hydrolyzate, e.g. B. maltodextrin, glucose, the dextrose equivalent of the starch hydrolyzate preferably being between 1 and 50, preferably between 3 and 35, particularly preferably between 3 and 20.
  • a soluble starch hydrolyzate e.g. B. maltodextrin, glucose
  • the dextrose equivalent of the starch hydrolyzate preferably being between 1 and 50, preferably between 3 and 35, particularly preferably between 3 and 20.
  • the components of the material system can be set differently in relation to one another.
  • the proportion of lignin in a printing fluid according to the disclosure can be between 10-35% (always based on the entire mixture), preferably 10-25%, more preferably 15-20%;
  • a starch hydrolyzate can be present individually or in a mixture of several components in a proportion of between 10-35% (always based on the total mixture), preferably 10-25%, more preferably 15-20%;
  • Dispersing additives and / or surfactants can be between 0 - 3% (always based on the total mixture), preferably 0.1-1%.
  • the alcohol content can be between 0.5% -15%, preferably 2% -10%, particularly preferably 5% -8% and / or where the alcohols comprise simple alcohols, diols or polyols or mixtures of these.
  • the viscosity of the pressure fluid is adjusted in a suitable manner with suitable substances or fluids known to the person skilled in the art.
  • the viscosity can be between 2 mPas-20 mPas, preferably between 8 mPas-15 mPas and particularly preferably between 10 mPas-14 mPas.
  • the printing fluid can also include surfactants such as sodium dodecyl sulfate or sodium laureth sulfate and a surface tension of 20 mN / m - 50 mN / m, preferably 25 mN / m - 40 mN / m and particularly preferably 28 mN / m - 35 mN / m, and / or defoamers from, for example, the group of siloxanes and / or colorants.
  • surfactants such as sodium dodecyl sulfate or sodium laureth sulfate and a surface tension of 20 mN / m - 50 mN / m, preferably 25 mN / m - 40 mN / m and particularly preferably 28 mN / m - 35 mN / m, and / or defoamers from, for example, the group of siloxanes and / or colorants.
  • the invention relates to a 3D printing method for producing a molded body, comprising the steps of applying a particle material mixture on a construction level, selective application of a printing fluid, the printing fluid comprising or consisting of a fluid selected from the group consisting of water or an aqueous solution and a lignin-containing component or derivatives thereof, preferably lignin sulfonate, for at least partial selective solidification, optionally tempering of the construction area or energy input into the applied particulate material mixture, preferably Tempering to 30.degree. C. to 60.degree. C., more preferably 40.degree. C. to 50.degree. C., and the pressure fluid, repeat these steps until the desired molded part has been obtained.
  • the molded parts (also mold or casting mold) produced in this way can serve as lamination molds or for all purposes in which the mold is to be removed again at the end of the process for which it is used. This can be done simply by adding water, so that the mold is flushed out and the product made with the mold can be gently freed from the mold.
  • the molded part obtained can be separated from the unsolidified particulate material mixture and the molded part can preferably be subjected to a further heat treatment step.
  • the particle material mixture is applied by means of a recoater and, if necessary, the particle material mixture is mixed together before application.
  • the printing fluid is selectively applied with a print head.
  • the molded part can be left in the powder bed under ambient conditions for 4 hours to 24 hours, preferably 8 hours to 15 hours, particularly preferably 10 hours to 11 hours, after the printing process has been completed. Further work steps can follow the 3D printing method according to the invention.
  • the molded part is subjected to a heat treatment; the molded part is preferably stored for 1 h to 7 h, preferably 4 h to 6 h, at 30 ° C to 160 ° C, preferably at 50 ° C to 140 ° C.
  • air can be sucked through the printed and non-printed building volume in order to increase the unpacking strength.
  • suction is started, preferably 1 h - 5 h, particularly preferably 1 h - 3 h after completion of the construction process.
  • the air drawn through can have a temperature that has changed from room temperature, the air drawn through preferably having a temperature of 10 ° C. to 80 ° C., preferably 15 ° C. to 60 ° C., particularly preferably 20 ° C. to 40 ° C.
  • the suction is preferably carried out for 0.5 h to 3 h, particularly preferably 1 h to 2 h.
  • a downstream heating process for the components in the furnace can still take place in order to further increase the strength.
  • the molded part is preferably stored for 1 hour to 7 hours, preferably 4 hours to 6 hours, at 30.degree. C.-160.degree. C., preferably at 50.degree. C.-140.degree.
  • the aftertreatment can also be carried out with microwave radiation in addition to or as a substitute for the heat treatment in the oven, the treatment taking place over a period of 2 to 30 minutes, preferably 2 to 15 minutes, particularly preferably 2 to 10 minutes.
  • a subsequent step in a 3D printing process according to the invention is to further coat or seal the surface of the molded part, in which case all methods and materials known to the person skilled in the art can be used for such molded parts.
  • the molded parts produced with the 3D printing process according to the invention can be used in a wide variety of applications. For example in lamination processes for the production of pipes or hoses for the aerospace industry or the like.
  • the material properties of the molded parts produced with the 3D process according to the invention are advantageous and certain material properties can be further influenced by suitable subsequent steps of the method.
  • the strength can be influenced on the one hand by the amount of water-soluble component in the printing fluid and the amount of printing fluid applied to the particulate material, on the other hand, the strength can be adjusted by leaving the molded part in the powder bed or a subsequent heat treatment, as well as the suction of air.
  • a molded part that is left in the powder bed for 4 hours to 24 hours, preferably 8 hours to 15 hours, particularly preferably 10 hours to 11 hours, under ambient conditions can have strengths of 80 N / cm 2 - 150 N / cm 2 in the direction of pressure. By sucking in air, the strength is reached after a short time.
  • the invention relates to the use of a molded part produced according to the invention or a molded part produced by a method according to the invention for the cold casting of synthetic resins or hydraulically setting systems or as a lamination mold.
  • the inert particulate material like that already in powder bed-based 3D printing
  • sands such as quartz sand, olivine sand, kerphalite or cerabeads, but also insoluble plastics, are not mixed with other soluble organic substances.
  • the advantage of the particle materials mentioned is that no changes to the existing coating technology are necessary and standard 3D printers can be used that are able to process particle material using the furan resin, phenolic resin and inorganic process.
  • the particle sizes are preferably between 90 ⁇ m and 250 ⁇ m, with finer powders also being suitable. This largely prevents segregation during the transport of the particulate material.
  • Mixed powders are usually homogenized in a discontinuous mixer upstream of the process.
  • the liquid second component i.e. a printing fluid
  • a print head which is guided in a meander shape over the coated first component, selectively according to the data of the respective layer image with a previously defined entry based on the weight of the particulate material.
  • the hydraulic fluid (the liquid component) consists largely of a solvent (solvent) that transfers the soluble material to the particulate material.
  • the solvent is preferably water.
  • the surface tension is increased from about 72 mN / m to preferably below 40 mN / m, particularly preferably between 30 mN / m and 35 mN / m by addition of a surfactant lowered. Only small amounts are added for this, as large amounts promote foam formation and nozzle failures can occur during printing. For this reason, only amounts of up to 1% of a surfactant such as sodium dodecyl sulfate, sugar surfactants, Surfynol® 440, Surfynol® 465 or Carbowet® 104 are added to the hydraulic fluid.
  • a surfactant such as sodium dodecyl sulfate, sugar surfactants, Surfynol® 440, Surfynol® 465 or Carbowet® 104 are added to the hydraulic fluid.
  • defoamers for example from the group of siloxanes such as TEGO ® Foamex 1488, and usually up to 0.5% of the pressure fluid is added.
  • the viscosity of the printing fluid is adjusted to a range of 4 mPas - 20 mPas by adding easily water-soluble alcohols. Preference is given to using polyhydric alcohols such as glycol, propylene glycol, polyethylene glycol, polyvinyl alcohol or soluble types of sugar which are present in up to 20%. An addition amount of 15% -20% maltodextrin is particularly preferred, resulting in a viscosity of 11 mPas-15 mPas.
  • polyhydric alcohols such as glycol, propylene glycol, polyethylene glycol, polyvinyl alcohol or soluble types of sugar which are present in up to 20%.
  • An addition amount of 15% -20% maltodextrin is particularly preferred, resulting in a viscosity of 11 mPas-15 mPas.
  • the dark, brown color of the printing fluid can be adjusted in its color by adding suitable colorants.
  • suitable colorants Small amounts of a readily soluble dye such as Basacide®, Orasole® or polymer dyes such as Milliken Red 17 are usually used. Usual amounts added are in the range between 0.1% - 0.5%, preferably 0.2% - 0.3%.
  • the construction platform is moved by one layer thickness relative to the printing unit and new powder material is applied.
  • An infrared lamp which is located on the recoater axis and / or has a separate axis and / or is mounted on the print head axis, can pass through the printed and / or the freshly applied layer heat one or more passes.
  • the increased temperature helps to reduce the amount of liquid again through evaporation.
  • the heating step also advantageously produces a higher level of contour sharpness, since the diffusion of the binder is reduced by the processes mentioned.
  • the surface temperature during the process is between 30 ° C and 60 ° C, preferably 40 ° C - 50 ° C.
  • 3 mm - 30 mm, preferably 10 mm, blank layers are applied in order to completely embed the components built last in loose material.
  • the component can be freed from loose material, for example by means of a suction device.
  • the unbound powder can be fed back into the process after a control sieving.
  • the components are then freed from the remaining material that is still adhering with compressed air.
  • the strengths of 80 N / cm 2 - 150 N / cm 2 are rather weak, but strong enough to handle them without destruction and deformation.
  • the 3D printed moldings have a porous surface, it is usually advantageous to treat the surface of the printed component before using it as a casting or lamination mold.
  • the porosity at the interface is reduced to such an extent that in the further application step the surface of the printed material no longer penetrates and the Cast or the laminate can be separated from the printed component.
  • the built form is put together or inserted into conventionally produced external forms and filled with a resin such as epoxy, polyurethane or polyester resin.
  • silicones or hydraulically setting material systems can also be used.
  • laminates based on glass or carbon fiber can be produced using the component surfaces.
  • the material systems After the material systems have cured, they are removed from the mold by bringing solvent, preferably water, into contact with the mold. This can be done, for example, by dipping or pouring.
  • solvent preferably water
  • the soluble component now dissolves quickly, the cohesion of the insoluble powder being broken.
  • the insoluble component is also flushed out, can be collected, mixed again with soluble material and fed back into the process. In order to release the built part, a sufficiently large gap is sufficient, from which the insoluble material can flow out together with the solvent.
  • 3D printing processes are all processes known from the prior art that enable components to be constructed as three-dimensional shapes and are compatible with the process components and devices described.
  • “selective pressure fluid application” can take place after each particle material or particle material mixture application or, depending on the requirements of the molded body and to optimize the production of the molded body, it can also be carried out irregularly, ie non-linearly and in parallel after each particle material application Pressure fluid application "can thus be set individually and in the course of the production of the molded body.
  • Binder within the meaning of the invention are materials which, when dissolved by a solution or a solvent, e.g. an aqueous solution, lead to solid and insoluble particles, e.g. sands, sticking together in a particle material and creating a relative strength between the particles.
  • a solution or a solvent e.g. an aqueous solution
  • Shaped body or “component” or “shape” or “3-D molded part” within the meaning of the invention are all three-dimensional objects produced by means of the method according to the invention (3-D printing method) which have dimensional stability.
  • powder-based 3D printing e.g. inkjet process
  • particle materials or “insoluble particle materials”
  • sand, ceramic powder, metal powder, plastics, wood particles, fiber materials, celluloses and / or lactose powder can be used as "particle materials” or "insoluble particle materials”, in particular sand, ceramic powder, metal powder, plastics, wood particles, fiber materials, celluloses and / or lactose powder.
  • the particulate material is preferably a dry, free flowing powder. However, a cohesive, cut-resistant powder can also be used.
  • Porate material or “particulate material mixture” within the meaning of the invention is understood to mean a material mixture of two or different materials, e.g. a water-soluble and a water-insoluble particulate material, the individual materials being further described in the present disclosure.
  • a "material system" within the meaning of the invention consists of various components which, in their interaction, allow the layered construction of molded parts; these different components can be applied and applied together or one after the other in layers become. Individual components such as binder components can be present in one or both material components and these then have an influence on, for example, the strength of the molded part produced.
  • a “printing fluid” within the meaning of the invention serves to be applied selectively to the applied particle material mixture and to selectively achieve the formation of a shaped body.
  • the printing fluid can contain binder materials, these binder materials can essentially only be present in the particle material mixture, essentially exclusively in the
  • a "pressure fluid" within the meaning of the invention comprises or consists of a liquid selected from the group consisting of water or an aqueous solution and a lignin-containing component or derivatives or modified lignins thereof, preferably ligninsulphonate.
  • Building space is the geometric location in which the bed of particulate material grows during the building process through repeated coating with particulate material.
  • the building space is limited by a floor, the building platform, walls and an open top surface, the building level.
  • Cast material in the sense of this inventor is any castable material, in particular those where no temperatures occur during processing that could weaken a cold resin bond and thus promote removal from the mold.
  • porosity is a labyrinth structure of cavities that is created between the particles connected in the 3D printing process.
  • the “sealing” acts on the geometric boundary between the printed form and the cavity to be filled. It closes the surface of the pores of the porous molded body.
  • Cold casting processes are to be understood in particular as casting processes in which the temperature of the casting mold and the core do not reach the decomposition or softening temperature of the molding material before, during and after casting.
  • the strength of the mold is not influenced by the casting would be metal casting processes in which the mold is generally slowly destroyed by the hot casting mass.
  • treated surface denotes a surface of the casting mold that is treated in a preferably separate step after printing and cleaning the mold. This treatment is often an application of a substance to the surface and thus also to the areas of the mold near the surface or the core. All conceivable different methods can be considered for the order.
  • One aspect of the present invention is to provide a mold, in particular for use in cold casting and lamination processes, which is produced by means of a powder-based layer construction process, the final form optionally having a treated surface and being weakened and demolded by a solvent.
  • the treated surface can, for example, prevent pourable material systems or liquid binders from penetrating the molded body due to the hydrostatic pressure or capillary effects.
  • the invention comprises a material system composed of a mixture of a particulate material, at least one powder component being soluble in a second liquid component.
  • the invention relates to a first one
  • Material component which consists of at least one insoluble inorganic and / or organic particle material and of a soluble, preferably water-soluble polymer with a similar particle size distribution.
  • the invention relates to a second one
  • Material component that largely consists of a solvent and additives to adjust the viscosity and surface tension.
  • the invention relates to the production of water-soluble forms by means of powder-bed-based 3D printing in the layer construction process and with a liquid component that is selectively introduced into the particle material.
  • the invention relates to a use of the mold according to the invention for the production of cold cast parts as a permanent mold or laminate.
  • the casting molds according to the invention can be used to produce concrete cast parts and / or cold-cast polymer components.
  • a powder bed-based 3D printing process is preferably used for the layer construction process.
  • the surface is optionally additionally sealed with a hydrophobic material, the penetration of the casting material into the pores of the casting mold can be well restricted.
  • a size and / or dispersion in particular a zirconium oxide, aluminum oxide, calcium oxide, titanium oxide, chalk or silica-based size and / or a plastic, cellulose, sugar -, flour and / or salt-based solution.
  • the porosity of the surface can be changed or sealed by a fat, oil, wax and / or warm water-soluble substances.
  • An exemplary apparatus for producing a molded part in accordance with the present invention includes a powder coater. With this, particulate material is applied to a building platform and smoothed.
  • the applied particulate material can consist of a wide variety of insoluble materials, preferred according to the invention and due to its low cost, however, is sand, which is water-soluble Polymer is mixed.
  • the height of the powder layers is determined by the build platform. It is lowered after applying a layer. During the next coating process, the resulting volume is filled and the supernatant is smoothed out. The result is a substantially or even almost perfectly parallel and smooth layer of defined height.
  • the layer is coated with a liquid using an inkjet print head, which transfers the soluble polymer onto the particle material.
  • the print image corresponds to the section through the component at the current height of the device. The liquid hits the particulate material and slowly diffuses into it.
  • the soluble binder physically binds the surrounding loose insoluble particles together.
  • the bond is initially only of low strength.
  • the construction platform is lowered by one layer thickness and the layer is additionally heated using heat.
  • the steps of layer formation, printing / exposure, heating and lowering are now repeated until the desired component is completely created.
  • the component is now completely in the powder cake.
  • loose particle material is removed from the component.
  • loose powder material can be cleaned using compressed air.
  • the bound building volume surrounded by unbound can be dried more quickly by sucking air through it.
  • C. The component produced can then be dried in the oven to further increase its strength. After the surface has been treated, the component can be used for cold casting or as a lamination mold.
  • insoluble particulate material and soluble polymer different mean grain sizes are used.
  • sand and soluble polymer with an average grain diameter of 60 m2 - 90 mhh are used, whereby the layer height of 150 m2 can be selected very finely.
  • Coarser particles with, for example, a dso 140 pm - 250 pm allow only 250 pm - 400 pm layer heights. This gives coarser surfaces.
  • the rate of build-up is also influenced by the fineness of the particulate material.
  • Particulate material consisting of sand with an average grain size of 150 ⁇ m (95%) and a sand with a dso of 190 ⁇ m (5%) is mixed in a nautical mixer for 1 h and then sieved (250 ⁇ m mesh size).
  • Particulate material consisting of softwood fibers (80%, e.g. Lignocel®) and starch powder (20%) are mixed in a nautical mixer for 1 h and then sieved (250 ⁇ m mesh size).
  • composition of an exemplary hydraulic fluid (liquid component)
  • At least Water is added in portions, lignosulfonate (25%), while stirring at 300 rpm using a paddle mixer, and the mixture is stirred until the solid is completely dissolved. Then maltodextrin (12%) and glucose (10%) are also added in portions, followed by Surfynol (0.8%) and finally Zetasperse 179 (0.2%). After stirring for a further hour at 600 rpm, the mixture is filtered (mesh size ⁇ 1 ⁇ m) (the quantities given relate to 100% of the total mixture).
  • the construction platform Before the actual printing, the construction platform is covered with a layer of foundry sand with an average grain size of 140 ⁇ m and heated to a surface temperature of 90 ° C. with the help of IR radiation. This is followed by the layered printing process, with printing fluid being introduced via the print head according to the construction data with an entry of 15% based on the mass of the particulate material.
  • the parts After the print job has been completed, negative pressure is applied to the box for 1 hour, with ambient air being drawn through the powder cake and the components being dried. After unpacking and finishing, the parts have a 3-point flexural strength of 210 N / cm 2 and a residual moisture of 0.3%. With a maximum rel. Humidity of 60%, the parts can be stored without deformation.
  • FIG. 1 shows the use of the water-soluble core (100) produced as a lamination mold with the laminate (101) already surrounding it. After the resin has cured, the mold is placed in a water basin (200) and washed out with a water jet (202) to assist.
  • FIG. 2 shows the dissolving form (300). The insoluble component of the particulate material (301) collects at the bottom of the water basin. After the soluble component has completely dissolved, the laminate (400) remains and can still be completely cleaned under a water jet (401) (FIG. 3).
  • Figure 4 shows the cleaned and dried laminate.
  • Figure 5 shows the application in cold casting. First, the water-soluble form (602) is placed in a form (601).
  • the material to be cast for example an epoxy resin or concrete (600), is cast into the mold. After the casting material has hardened, usually after 24 hours, the core is again demolded under mild conditions by means of a dip basin and / or water jet (604). The remaining insoluble material can be fed back into the printing process after drying and adding the soluble component. This makes the process very economical, which is a great advantage, especially when using special sands.

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  • Manufacturing & Machinery (AREA)
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  • Physics & Mathematics (AREA)
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  • Inorganic Chemistry (AREA)
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  • Toxicology (AREA)
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Abstract

La présente invention concerne un système de matériau pour impression 3D, un procédé d'impression 3D utilisant un composant contenant de la lignine ou de ses dérivés ou de lignines modifiées, des moulages solubles qui sont produits par un procédé de fabrication de couche d'additif à base de poudre et l'utilisation des moulages.
EP20816382.4A 2019-11-01 2020-10-29 Procédé d'impression 3d et moulage produit par ce procédé à l'aide de lignosulfonate Pending EP4051652A1 (fr)

Applications Claiming Priority (2)

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DE102019007595.1A DE102019007595A1 (de) 2019-11-01 2019-11-01 3d-druckverfahren und damit hergestelltes formteil unter verwendung von ligninsulfat
PCT/DE2020/000263 WO2021083446A1 (fr) 2019-11-01 2020-10-29 Procédé d'impression 3d et moulage produit par ce procédé à l'aide de lignosulfonate

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EP4051652A1 true EP4051652A1 (fr) 2022-09-07

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CN107109803B (zh) * 2014-12-22 2020-01-03 赛尔怀斯公司 工具或工具零件、包括这种工具或工具零件的系统、生产这种工具或工具零件的方法以及从浆状物浆料模制产品的方法
DE102019004176A1 (de) 2019-06-14 2020-12-17 Voxeljet Ag Verfahren und Vorrichtung zum Herstellen von 3D-Formteilen mittels Schichtaufbautechnik und Beschichter mit Unterdruckverschluss
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DE102019007595A1 (de) 2019-11-01 2021-05-06 Voxeljet Ag 3d-druckverfahren und damit hergestelltes formteil unter verwendung von ligninsulfat
DE102019007863A1 (de) 2019-11-13 2021-05-20 Voxeljet Ag Partikelmaterialvorwärmvorrichtung und Verwendung in 3D-Verfahren

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CN115279712A (zh) 2022-11-01
US20220371267A1 (en) 2022-11-24
US11820076B2 (en) 2023-11-21
US20240083110A1 (en) 2024-03-14
DE102019007595A1 (de) 2021-05-06

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