EP3727801A1 - Procédé pour fabriquer un objet imprimé en 3d traité - Google Patents

Procédé pour fabriquer un objet imprimé en 3d traité

Info

Publication number
EP3727801A1
EP3727801A1 EP18816133.5A EP18816133A EP3727801A1 EP 3727801 A1 EP3727801 A1 EP 3727801A1 EP 18816133 A EP18816133 A EP 18816133A EP 3727801 A1 EP3727801 A1 EP 3727801A1
Authority
EP
European Patent Office
Prior art keywords
temperature
article
binder
particles
liquid
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
EP18816133.5A
Other languages
German (de)
English (en)
Inventor
Dirk Achten
Thomas BÜSGEN
Roland Wagner
Jonas KÜNZEL
Michael Kessler
Bettina METTMANN
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.)
Stratasys Inc
Original Assignee
Covestro Deutschland 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 Covestro Deutschland AG filed Critical Covestro Deutschland AG
Publication of EP3727801A1 publication Critical patent/EP3727801A1/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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/105—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing inorganic lubricating or binding agents, e.g. metal salts
    • 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
    • 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
    • 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
    • B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
    • B29C71/02—Thermal after-treatment
    • 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
    • B33Y80/00—Products made by additive manufacturing
    • 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
    • B22F10/30—Process control
    • B22F10/38—Process control to achieve specific product aspects, e.g. surface smoothness, density, porosity or hollow structures
    • 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
    • B22F10/62—Treatment of workpieces or articles after build-up by chemical means
    • 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
    • B22F2302/00—Metal Compound, non-Metallic compound or non-metal composition of the powder or its coating
    • B22F2302/25—Oxide
    • B22F2302/253—Aluminum oxide (Al2O3)
    • 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
    • B22F2302/00—Metal Compound, non-Metallic compound or non-metal composition of the powder or its coating
    • B22F2302/25—Oxide
    • B22F2302/256—Silicium oxide (SiO2)
    • 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
    • B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
    • B29C71/02—Thermal after-treatment
    • B29C2071/027—Tempering, i.e. heating an object to a high temperature and quenching it
    • 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
    • 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

Definitions

  • the present invention relates to a process for the preparation of a treated article comprising the steps of: depositing a layer of particles on a target surface; Applying a liquid binder to a selected portion of the layer corresponding to a cross-section of the article so that the particles are joined in the selected part; Repeating the steps of applying and applying binder to a plurality of layers such that the bonded portions of the adjacent layers combine to obtain an article, wherein at least a portion of the particles comprise a meltable polymer.
  • the invention further relates to a treated article obtainable by the process according to the invention.
  • Additive manufacturing processes are processes by which objects are built up in layers. They therefore differ significantly from other methods of manufacturing objects such as milling or drilling. In the latter method, an article is processed so that it receives its final geometry by removal of material.
  • Additive manufacturing processes use different materials and process techniques to build objects in layers.
  • FDM Fused Deposition Modeling
  • a thermoplastic plastic wire is liquefied and laid in layers on a mobile construction platform with the aid of a nozzle.
  • FDM Fused Deposition Modeling
  • a solid object is created.
  • the control of the nozzle and the build platform is based on a CAD drawing of the object. If the geometry of this object is complex, for example with geometric undercuts, support materials must be printed in addition and removed after completion of the object.
  • thermoplastic powders to build up objects in layers.
  • thin powder layers are applied via a so-called coater and then selectively melted by means of an energy source.
  • the surrounding powder supports the component geometry. Complex geometries are thereby more economical to produce than in the previously described FDM process.
  • various items can be packed or made tightly packed in the so-called powder bed.
  • powder-based additive manufacturing processes are among the most economical additive manufacturing processes on the market. They are therefore used predominantly by industrial users. Examples of powder-based additive manufacturing processes are the so-called laser sintering (SLS, Selective Laser Sintering) or high-speed sintering (HSS).
  • the energy input occurs over a steered laser beam.
  • HSS high-speed sintering
  • IR infrared
  • SHS selective heat sintering
  • thermoplastic materials used Based on the polymers that are predominantly used today in powder-based additive manufacturing processes, articles are produced whose mechanical properties can fundamentally differ from the characteristics of the materials known in other plastics-processing processes, such as injection molding. During processing by the additive manufacturing processes, the thermoplastic materials used lose their specific characteristics.
  • PA 12 Polyamide 12
  • PA12 is currently the most widely used material for powder-based additive manufacturing processes, such as e.g. the laser sinter.
  • PA12 is characterized by high strength and toughness when processed by injection molding or extrusion.
  • a commercially available PA12 exhibits an elongation at break of more than 200% after injection molding.
  • PA 12 articles produced by the laser sintering process show elongations at break of 15%.
  • the component is brittle and therefore can no longer be regarded as a typical PA12 component.
  • PP polypropylene
  • This material also embrittles and thus loses the PP-typical tough-elastic properties. Reasons for this can be found in the morphology of the polymers.
  • an irregular internal structure of the so-called semi-crystalline polymers arises.
  • the internal structure (morphology) of semicrystalline polymers is characterized in part by high order. A certain portion of the polymer chains forms crystalline, tightly packed structures upon cooling. During melting and cooling, these crystallites grow irregularly at the boundaries of the unfused particles as well as at the former grain boundaries of the powder particles and additives contained in the powder. The irregularity of the resulting morphology favors the formation of cracks under mechanical stress. The unavoidable residual porosity in the powder-based additive process promotes crack growth.
  • US 2005/0080191 A1 relates to a powder system for use in solid freeform production processes, comprising at least one polymer having reactive properties and fusible properties, wherein the at least one polymer is selected to react with a liquid binder and at a temperature above the melting point or the glass transition temperature of the at least one polymer is meltable.
  • the at least one polymer may comprise at least one reactive polymer and at least one fusible polymer, and the at least one fusible polymer may have a melting point or a glass transition temperature in the range of about 50 ° C to about 250 ° C.
  • a method for producing a treated article comprises the steps of:
  • the resulting article is contacted at least partially with a liquid heated to> T or heated to> T to obtain the treated article, where T is a temperature of> 25 ° C, the liquid for the binder present in the article and the fusible polymer is not a solvent or reactant and the powder bed is different from the particles of the fusible polymer.
  • annealing The contacting of the article with the heated liquid or the heated powder bed is hereinafter also referred to as annealing.
  • an object is built up in layers. If the number of recoveries for orders and irradiation is sufficiently small, it is also possible to speak of a two-dimensional object that is to be set up. Such a two-dimensional object can also be characterized as a coating. For example, for the construction of> 2 to ⁇ 20 repetitions for orders and irradiation can be performed.
  • the particles comprise a meltable polymer.
  • all particles used in the process to a meltable polymer are further preferred.
  • at least 90% by weight of the particles have a particle diameter of ⁇ 0.25 mm, preferably ⁇ 0.2 mm, particularly preferably ⁇ 0.15 mm.
  • the particles with the meltable polymer may, for example, be of homogeneous composition, so that there are no further fusible polymers in the particles.
  • Suitable powders of thermoplastic materials can be prepared by various common processes, such as milling, cryomilling, precipitation, spray drying, and others.
  • Suitable fusible polymers for the process according to the invention are, for example, all known thermoplastics which can be bonded with an adhesive having an adhesive force of> 0.5 N / mm 2 (tensile shear test in accordance with DIN EN 1465).
  • the particles may contain other additives such as fillers, stabilizers and the like, but also other polymers.
  • the total content of additives in the particles may be, for example,> 0.1% by weight to ⁇ 40% by weight, preferably> 1% by weight to ⁇ 20% by weight.
  • Suitable binders are physically setting adhesives and chemically hardening adhesives.
  • the binder may be, for example, an aqueous dispersion adhesive, a solvent-containing wet adhesive, a polymerization adhesive, a polycondensation adhesive or a polyaddition adhesive.
  • the binder is preferably applied via a digital application method.
  • This can be a drop-on-demand process, a screen printing process (with layer-wise changeable masks), an inkjet process or another easily controllable metering process.
  • a digital printing method such as the Inkj etclar.
  • the liquid for the present in the subject binder and the meltable polymer is not a solvent or reactant.
  • binder present in the article includes compounds derived from the binder formed by physical processes such as evaporation of a solvent or chemical processes such as crosslinking or polymerization reactions, and as Glue the particles together.
  • No solvent means in particular that the solubility of the considered component in the liquid at 20 ° C ⁇ 10 g / L, preferably ⁇ 1 g / L, more preferably ⁇ 0.1 g / L and particularly preferably ⁇ 0.01 g / L. Furthermore, particularly suitable liquids do not lead to any unwanted discoloration of the article and allow the article to swell only reversibly or preferably not at all.
  • Particularly suitable liquids are further distinguished by the fact that they can be repeatedly heated to the exten sion temperature of the thermoplastic without showing degradation phenomena.
  • the surface tension of the liquid is at least 10 mN / m less than or greater than the surface tension of the thermoplastic material of the component.
  • low-volatile apolar liquids which can be heated under pressure to the desired temperatures, but then slightly from the obtained, treated object to be removed.
  • the article Upon receipt of the article, it may further be further strengthened by conventional post-processing techniques such as coating or infusing with suitable coating or infusion agents such as an aqueous polyurethane dispersion followed by drying and curing at temperatures below or below 20 ° C below the softening temperature of the thermoplastic powder before it comes into contact with the inert liquid or the inert powder material.
  • suitable coating or infusion agents such as an aqueous polyurethane dispersion followed by drying and curing at temperatures below or below 20 ° C below the softening temperature of the thermoplastic powder before it comes into contact with the inert liquid or the inert powder material.
  • the article obtained after the additive manufacturing process is at least partially contacted by a heated liquid or a heated powder bed. In this case, the resulting article remains fonnstabil by the binder and the bonded powder particles can be sintered to the treated article.
  • This new inventive method has several advantages over the prior art or conventional selective laser sintering or high speed sintering method.
  • the installation space temperature may be low, as in a method analogous to binder jetting.
  • the only requirement is that the adhesive hardens sufficiently.
  • the subsequent, but spatially separable sintering processes can be significantly simplified and offered cheaper, since no heated space is necessary.
  • the products of several building processes can be sintered together in a subsequent process, which again increases the flexibility and cost-efficiency of the construction process.
  • the method according to the invention can produce materials with higher density and hardness than conventional sintering methods, since the binder prevents a part of the porosity which arises in a normal sintering process.
  • the inventive method also allows the processing of almost any thermoplastic powders, since the problems of the installation space process in the SLS and HS process do not occur.
  • non-crystalline thermoplastics can also be processed into mechanically high-quality components.
  • the temperature of the liquid is preferably set to a value of ⁇ 20 ° C., preferably ⁇ 50 ° C., particularly preferably ⁇ 80 ° C., slowly within> 20 min, preferably> 40 min, particularly preferably> 60 min below the softening temperature, and the treated body is obtained. Subsequently, the body can be washed, if desired.
  • the temperature of the liquid is preferably after sintering to a value of ⁇ 20 ° C, preferably ⁇ 50 ° C, more preferably> 80 ° C within ⁇ 15 min, preferably ⁇ 10 min, more preferably ⁇ 5 Lowered below the supernatant temp eratur and the treated received in body. Subsequently, the body can be washed, if desired. This method is particularly preferred when sintering amorphous materials.
  • the binder selected is a binder which cures with crosslinking. Covalent bonds are then formed during curing of the binder, which at least partially lead to a spatial network structure in the cured binder.
  • the binder is selected from: radiation-curing binders, binders which cure by radical initiator, binders which increase through exposure to increasing temperature, two-component reactive binders and mixtures of the abovementioned binders and curing variants.
  • Preferred are binders based on (meth) acrylates, isocyanates, polyurethanes, epoxides, or cyanoacrylates or mixtures of at least two thereof.
  • the binder present in the article for example after crosslinking or film formation, has a softening temperature which is greater than the softening temperature of the meltable polymer, wherein the softening temperature is defined as the intersection of the curves for memory modulus E 'and loss modulus E "in one Temp-dependent dynamic-mechanical analysis.
  • the adhesive present in the article (for example after crosslinking or film formation) in the tensile shear test according to DIN EN 1465 has an adhesive force of> 0.5 N / mm 2 (preferably> 1 N / mm 2 ) in the bonding of test specimens of the fusible polymer, more preferably> 2 N / mm 2 ).
  • the liquid is at least temporarily pressurized.
  • the pressure (relative, ie overpressure) is preferably> 1 bar to ⁇ 100 bar, preferably> 2 bar to ⁇ 50 bar, particularly preferably> 3 bar to ⁇ 20 bar and very particularly preferably> 4 bar to ⁇ 10 bar.
  • the pressure impact can be carried out in suitable autoclave made of glass or metal by means of pressing a suitable gas or by mechanical reduction of the autoclave volume.
  • pressurizing the liquid with overpressure can the temperature of the heated liquid can be lowered compared to process variants without pressurization, for example by> 5 ° C or> 10 ° C.
  • the temperature T expressed in degrees Celsius, is> 1 ° C, preferably> 2 ° C, more preferably> 5 ° C below the softening temperature of the meltable polymer, wherein the softening temperature is defined as the intersection of the curves for storage modulus E 'and loss modulus E "in a temperature-dependent dynamic-mechanical analysis.
  • the temperature T expressed in degrees Celsius, further ⁇ 95% (preferably ⁇ 90%, more preferably ⁇ 85%) of the decomposition temperature of the binder after crosslinking, wherein the Z set temperature is defined as the temperature, at a mass loss of> 10% is detected in a thermogravimetric analysis at a heating rate of 5 ° C / min in the air stream.
  • the temperature T is selected so that at this temperature the modulus of elasticity E ', determined by means of dynamic mechanical analysis of the fusible polymer, is> 10 5 Pa to ⁇ 10 8 Pa, preferably> 5 ⁇ 10 5 Pa to ⁇ 5 ⁇ 10 7 Pa, more preferably> 1 ⁇ 10 6 Pa to ⁇ 1 ⁇ 10 7 Pa.
  • contacting the resulting article with the liquid or powder bed is carried out for> 5 minutes to ⁇ 24 hours, preferably> 30 minutes to ⁇ 18 hours, more preferably> 1 hour to ⁇ 12 hours.
  • the temperature is T> 40 ° C to ⁇ 300 ° C, preferably> 50 ° C to ⁇ 280 ° C and more preferably> 80 ° C to ⁇ 250 ° C.
  • the meltable polymer is selected from: PEEK, PAEK, PEKK, polyethersulfone, polyimide, polyetherimide, polyester, polyamide, polycarbonate, polyurethane, polyvinyl chloride, polyoxymethylene, polyvinyl acetate, polyacrylate, polymethacrylate, TPE (thermoplastic elastomers), polystyrene, Polyethylene, polypropylene or mixtures of at least two of said polymers.
  • the meltable polymer is a polyurethane which is at least proportionally available from the reaction of aromatic and / or aliphatic polyisocyanates with suitable (poly) alcohols and / or (poly) amines or mixtures thereof.
  • suitable (poly) alcohols and / or (poly) amines or mixtures thereof Preference is given, at least in part, to using (poly) alcohols from the group consisting of: linear polyesterpolyols, polyetherpolyols, polycarbonatepolyols, polyacrylatepolyols or a combination of at least two thereof. In a preferred embodiment, these carry (poly) alcohols or (Poly) amine terminal alcohol and / or amine functionalities.
  • the (poly) alcohols and / or (poly) amines have a molecular weight of 52 to 10,000 g / mol.
  • these (poly) alcohols or (poly) amines as starting materials have a melting point in the range of 5 to 150 ° C.
  • Preferred polyisocyanates which can be used, at least in part, for the preparation of the fusible polyurethanes are TDI, MDI, HDI, PDI, H12MDI, IPDI, TODI, XDI, NDI and decane diisocyanate.
  • Particularly preferred polyisocyanates are HDI, PDI, H12MDI, MDI and TDI.
  • meltable polymer is a bisphenol A and / or bisphenol TMC based polycarbonate.
  • the liquid is selected from: silicone oils, fluorinated hydrocarbons, polyethylene waxes, salt water, molten metals, ionic liquids and mixtures of at least two of said liquids.
  • salt water a saturated NaCl solution is preferred.
  • the powder bed contains particles of glass, polytetrafluoroethylene, silicon dioxide, aluminum oxide, metals low and high-melting salts, water-soluble salts, acid-soluble salts, base-soluble salts or mixtures of at least two thereof. Powders having a high heat conductivity of> 0.2 WHT'K 1 are particularly preferred. The ability to adapt can be determined as described in the publication TK04 Application Note, 2015, TeKa, Berlin, Germany "Testing fragments and powder".
  • the binders may be present as aqueous dispersions, solvent adhesives or 100% reactive adhesives.
  • reactive adhesives are adhesives which react either by reacting the adhesive components with themselves to form new compounds and / or by reacting the adhesive components with the powders to form new compounds. The reactions may be reacted by contacting the components with themselves and / or the powder and / or by heat and / or by catalyst addition (catalyst activation) and / or by radiation activation and / or by drying the solvent or dispersion to form a film.
  • Adhesives belong to the meaning of Invention to the binders and are used partly synonymous.
  • Metallpulvem When using Metallpulvem is preferably carried out under inert gas or at least surface-oxidized or oxidation-resistant metal powder are used to exclude metal fires. Examples of particularly suitable combinations of metals and suitable binders and powders in the process according to the invention are listed below. Again, the process is preferably carried out under inert conditions, for example by using inert gas:
  • the present invention further relates to a treated article obtainable by a process as described in detail above.
  • Such an article may in particular have improved mechanical properties.
  • the article produced according to the method of the invention preferably has a surface with a mean roughness Ra (DIN EN ISO 4287) of ⁇ 500 mih, preferably of ⁇ 200 mih, or preferably of ⁇ 100 mih or preferably in a range of 10 to 500 mih, or more preferably in a range of 50 to 100 mih.
  • Ra mean roughness
  • the article produced by the process according to the invention is distinguished in particular by its particularly high stability and, furthermore, by particularly homogeneous mechanical properties.
  • the density and the tensile strength are mentioned, which in particular represents the stability of the article in the layer plane.
  • the product of the method according to the invention has a tensile strength which is greater than the tensile strength of the untempered article.
  • the treated articles after annealing, the treated articles have a tensile strength that is greater than before annealing.
  • the treated articles after annealing, have a tensile strength which is greater than the tensile strength of the untreated article, preferably by an amount of> 10%, more preferably by an amount of> 20%, more preferably by one Amount of> 30%, more preferably by an amount of> 50%, more preferably by an amount of> 100%, wherein the values described above relate to the tensile strength of the untreated article or the article before annealing.
  • the density of the treated article is greater than the density of the untreated article, or in other words, that the density after annealing is greater in a suitable medium according to the present invention than before annealing.
  • the difference in density is typically expressed by the fact that the tempered product or object has smaller geometrical dimensions than the unannealed object.
  • the density of the treated article is greater than the density of the untreated article, preferably by an amount of> 1%, preferably by an amount of> 2%, more preferably by an amount of> 5%, on preferably by an amount of> 10%, based on the density of the untreated article or based on the density of the article before annealing.
  • the layers of the treated body to each other have a shear strength of> 1 N / mm 2 (preferably> 1.5 N / mm 2 , more preferably> 2 N / mm 2 ).
  • Test method Tensile test: According to DIN EN ISO 527-2.
  • Particle sizes or particle diameters Unless otherwise specified, particle sizes or particle sizes were determined by means of laser diffraction (HELOS particle size enanaly s e)
  • Silicone oil (silicone oil bath): Oil M 50 El from the company Momentive TM, colorless NaCl: table salt with grain size from 0.1 to 0.9 mm.
  • Sand quartz sand with grain size from 0.4 to 0.8 mm.
  • Polycarbonate Makroion® 2408 was purchased from Covestro Deutschland AG.
  • Polyurethane adhesive Dispercoll® U54, 50% polyurethane adhesive dispersion was purchased from Covestro Deutschland AG.
  • Part of the resulting PMMA-based S1 rods were completely enveloped with powdered NaCl, with the rods each being enclosed in the direction of space by at least one 1 cm thick salt layer and heated at 140 ° C. and 160 ° C. for 2 h and 4 h in a circulating air oven. This process is also called annealing. Following annealing, the vessel was removed from the convection oven with NaCl powder and tensile bars and slowly cooled to 23 ° C over 30 minutes before the bars were removed and mechanically separated from the salt.
  • the TPU powder used was obtained by cryomilling Desmopan® 3787A, obtained from Covestro GmbH AG.
  • the TPU was mixed with 0.2% by weight, based on TPU, of hydrophobized pyrogenic silica as flow agent (Aerosil® R972 from Evonik), and the mixture was mechanically converted into powder under cryogenic cryogenization (cryogenic comminution) in a pin mill Screening machine classified.
  • 90% by weight of the composition had a particle diameter of less than 140 ⁇ m (measured by means of laser diffraction (HELOS particle size analysis)).
  • the bars were in the direction of space in each case surrounded by at least one 1 cm thick salt layer and heated for 1 h at 180 ° C in a convection oven (annealing). Following annealing, the vessel was removed from the convection oven with NaCl powder and sample rods and cooled to 23 ° C over 30 minutes before the bars were removed and mechanically separated from the salt. The rods obtained were then tested after storage for 24 h in accordance with DIN EN ISO 527-2 (the test specimens do not conform to DIN EN ISO 527-2) in the tensile test.
  • the polycarbonate powder used was obtained by cryomilling Makrolon® 2408, purchased from Covestro GmbH AG.
  • the polycarbonate with 0.2 wt .-%, based on polycarbonate, hydrophobi erter fumed silica as a superplasticizer (Aerosil® R972 from Evonik) was mixed and the mixture processed mechanically under deep freezing (cryogenic comminution with liquid nitrogen) in a pin mill to powder and then classified by a screening machine.
  • 90% by weight of the composition had a particle diameter of less than 140 ⁇ m (measured by means of laser diffraction (HELOS particle size analysis)).
  • the plate obtained was cut in about learning * 8 cm rods and a part of the rods obtained according to the invention coated with powdered NaCl, the rods in the direction of each of at least a schles thick salt layer were enclosed and heated for lh at 180 ° C in a convection oven.
  • the vessel was removed from the convection oven with NaCl powder and sample rods and cooled to 23 ° C over 30 minutes before the bars were removed and mechanically separated from the salt.
  • the density of the samples re-tempered according to the invention has increased, which is to be deduced from the lower heights and widths of the sample body after tempering.
  • the surface roughness of the samples post-annealed according to the present invention tends to be improved toward a lower surface roughness. This was determined by haptic tests on the surfaces. This effect is particularly evident when using non-dissolving and swelling tempering liquids or fine powders.

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  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
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Abstract

L'invention concerne un procédé pour fabriquer un objet traité comprenant les étapes consistant à : appliquer une couche de particules sur une surface cible ; appliquer un liant liquide sur une partie sélectionnée de la couche, conformément à une section de l'objet, de sorte que les particules de la partie sélectionnée soient liées, et répéter la première étape d'application et l'étape d'application d'un liant pour une pluralité de couches, de sorte que les parties liées des couches voisines soient liées, de manière à obtenir l'objet, au moins une partie des particules présentant un polymère fusible. On choisit de préférence comme liant un liant qui durcit par réticulation. L'objet obtenu est mis en contact au moins en partie avec un liquide chauffé à ≥ T ou avec un lit de poudre chauffé à ≥ T pour obtenir l'objet traité. T désigne une température ≥ 25 °C ; le liquide ne désigne ni un solvant ni un partenaire réactionnel pour le liant présent dans l'objet et le polymère fusible, et le lit de poudre est différent des particules du polymère fusible. L'invention concerne également un objet traité pouvant être obtenu par le procédé selon l'invention.
EP18816133.5A 2017-12-19 2018-12-18 Procédé pour fabriquer un objet imprimé en 3d traité Pending EP3727801A1 (fr)

Applications Claiming Priority (2)

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EP17208280 2017-12-19
PCT/EP2018/085547 WO2019121718A1 (fr) 2017-12-19 2018-12-18 Procédé pour fabriquer un objet imprimé en 3d traité

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EP3727801A1 true EP3727801A1 (fr) 2020-10-28

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CN112280082A (zh) * 2020-10-29 2021-01-29 江苏集萃先进高分子材料研究所有限公司 一种基于选择性激光烧结后处理的着色方法
EP4101872A1 (fr) * 2021-06-07 2022-12-14 Covestro Deutschland AG Procédé pour fabriquer un objet au moins en partie revêtu
EP4330304A1 (fr) * 2021-04-26 2024-03-06 Stratasys, Inc. Procédé permettant de produire un objet au moins partiellement revêtu
EP4108362A1 (fr) 2021-06-22 2022-12-28 Evonik Operations GmbH Système de matière pour l'impression 3d
EP4108692A1 (fr) 2021-06-22 2022-12-28 Evonik Operations GmbH Système de matière pour l'impression 3d
EP4108361A1 (fr) 2021-06-22 2022-12-28 Evonik Operations GmbH Système de matière pour l'impression 3d
CN115635677A (zh) * 2022-10-28 2023-01-24 哈尔滨工业大学 一种快速固化双组分粘结剂喷射3d打印的方法

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US11833749B2 (en) 2023-12-05
US20200306829A1 (en) 2020-10-01
WO2019121718A1 (fr) 2019-06-27

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