WO2002102576A1 - Procede pour realiser des modeles tridimensionnels par frittage selectif au laser - Google Patents

Procede pour realiser des modeles tridimensionnels par frittage selectif au laser Download PDF

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Publication number
WO2002102576A1
WO2002102576A1 PCT/EP2002/006138 EP0206138W WO02102576A1 WO 2002102576 A1 WO2002102576 A1 WO 2002102576A1 EP 0206138 W EP0206138 W EP 0206138W WO 02102576 A1 WO02102576 A1 WO 02102576A1
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WO
WIPO (PCT)
Prior art keywords
laser sintering
thermoplastic particles
sintering
particles
laser
Prior art date
Application number
PCT/EP2002/006138
Other languages
German (de)
English (en)
Inventor
Wolfgang Podszun
Thomas Seul
Artur Martin Osmanda
Ernst Schmachtenberg
Original Assignee
Bayer Aktiengesellschaft
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 Bayer Aktiengesellschaft filed Critical Bayer Aktiengesellschaft
Publication of WO2002102576A1 publication Critical patent/WO2002102576A1/fr

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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
    • B29C64/141—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
    • 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
    • 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

Definitions

  • the invention relates to a method for rapid prototyping by laser sintering using surface-modified powders made of thermoplastics.
  • Rapid prototyping is the term used to summarize the computer-controlled additive, automatic model building methods known today.
  • Laser sintering is a rapid prototyping process in which fillings made of certain powdery materials under the action of laser beams, which are preferably controlled by a program, layer by layer on certain
  • thermoplastic powders for laser sintering by means of lasers is known (A. Gebhardt, rapid prototyping, Carl Hanser Verlag, Kunststoff, Vienna 2000, page 127).
  • a method for producing model bodies is described in which any three-dimensional structure can be built up by selective sintering using finely divided thermoplastics with the aid of light from a laser, for example a CO 2 or ND / YAG laser.
  • thermoplastic or plastic powder in which the individual particles are spherical, are particularly well suited for laser sintering.
  • WO / 97/29148 describes the production of spherical particles from styrene and acrylate polymers by spray drying, and the use of the products obtained for laser sintering.
  • the density, surface quality, level of detail and contour accuracy of the model in rapid prototyping by laser sintering are largely determined by the properties of the polymer powder.
  • the polymer powders currently used have unsatisfactory results in certain applications, i.e. poor surface quality, low level of detail and low contour accuracy. This disadvantage requires extensive reworking of the prototype in order to achieve the surface finish required in practice.
  • thermoplastic powders used tend to agglomerate during storage and when used due to the elevated temperature even without laser exposure. Because of this agglomeration tendency, the powders used in a laser sintering process, but not used for model generation, can only be partially used in a subsequent laser sintering process. For this reason, new powders that have not yet been used in a laser sintering process are added to the reused powders.
  • the object of the present invention is to provide thermoplastic particles for laser sintering, which lead to moldings with improved surface quality, greater level of detail and increased contour accuracy. Another object is to provide thermoplastic particles which have a lower tendency to agglomerate at the unexposed areas in the laser sintering process.
  • the present invention relates to a method for producing three-dimensional patterns by laser sintering using thermoplastic particles with an average particle size of 5-250 ⁇ m for rapid prototyping by laser sintering, which is characterized in that the surface of the
  • Particles are modified prior to laser sintering to reduce their wettability.
  • thermoplastics are the usually thermoplastically processable polymers for the process, for example its polystyrene, polyacrylates, polycarbonate, thermoplastic polyurethanes, polyamides and polyesters.
  • Semi-crystalline thermoplastics are preferably used.
  • semi-crystalline thermoplastics are synthetic polymers which have at least partial crystallinity at room temperature and melt in the range from 100 to 300.degree. Thermoplastics from the group of polyamides, polyesters and polyurethanes are preferred. Polyamide-6,6, polyamide-6,10, polyamide-6, polyamide-7, polyamide-8, polyamide-9, polyamide-11, polyamide-12, and corresponding copolymers of these components are used as partially crystalline polyamides. Polyamide-11 and polyamide-12 are particularly preferred.
  • the particle size of the thermoplastic particles is 5-250 ⁇ m, preferably 10-100 ⁇ m.
  • the weight average is given here for determining the particle diameter (particle size).
  • the thermoplastic particles can have a narrow or wide particle diameter distribution. Thermoplastic particles with a narrow particle diameter distribution are advantageous for special applications.
  • the thermoplastic particles can have an irregular shape, for example a splinter shape or a spherical shape. The use of particles in spherical form has advantages, for example in relation to the flowability of the powder and pore volume of the models.
  • the method is preferably used in isothermal laser sintering.
  • the wettability of these particles is reduced by modifying the surface of the thermoplastic particles.
  • wettability means the tendency of a liquid to cover the surface.
  • the contact or contact angle can be used for a quantitative description of the wettability.
  • the contact angle can generally take values between 0 ° and 180 °, the value 0 ° standing for complete wetting (spreading) and 180 ° for no wetting.
  • the contact angle can e.g. from the surface energy, which is calculated according to the Washburn method, which is measured directly on powders. Further details of this method are from Christopher Rulison; Competitiveness studies for porous solids including powders and fibrous materials; Technical Note # 302, company Krüss USA, Hamburg.
  • the surface modification should preferably change the contact angle by at least
  • the size of the contact angle is a function of the wetting liquid.
  • N-methyl-2-pyrrolidone is also a meaningful test liquid because the surface tension of N-methyl-2-pyrrolidone at room temperature has the same value as molten polyamide 12, a particularly important material for laser sintering, at the melting temperature of the
  • PA 12 The contact angle is increased by the surface modification.
  • All fundamentally known physical and chemical methods for reducing the wettability can be used for the modification.
  • physical methods include, in particular, ultrasound treatment and treatment with electromagnetic radiation of different wavelengths or with particle radiation (electron radiation). Corona and plasma treatments are also other physical methods for surface modification.
  • Suitable surfactants are listed in "Surfactants Europe, A. Directory of Surface Acitive Agents available in Europe” (Edited by Gordon L. Hollis, Royal Society of Chemistry, Cambridge (1995)). Surfactants with a linear or branched C 6 to C 2 alkyl group, surfactants with siloxane units are also used, and fluorosurfactants, in particular surfactants with a C 4 to ds perfluoroalkyl radical, are particularly suitable.
  • the amount of surfactant is in particular 0.001% by weight to 5% by weight, preferably 0.01% by weight to 1% by weight, based on the thermoplastic particles.
  • thermoplastic particles with surfactant takes place in the surface modification of the thermoplastic particles with surfactant
  • water is a suitable solvent.
  • the solvent can be evaporated, if necessary if removed at an elevated temperature of 100 ° C or using reduced pressure, for example 5 to 200 torr.
  • Suitable surface-active polymer compounds for the treatment of the thermoplastics are polymers which are soluble in non-aqueous solvents and have a molecular weight of 2,000 to 1,000,000. Polymers with a proportion of polymerized units of Cg to C 22 alkyl (meth) acrylates and / or vinyl esters of Cs to C 22 carboxylic acids are preferred. Polymers with polymerized units of stearyl methacrylate, lauryl methacrylate and vinyl stearate may be mentioned as examples. Copolymers of C 8 -C 22 -alkyl (meth) acrylates or vinyl esters of C 8 -C 2 -carboxylic acids with hydrophilic monomers are particularly suitable.
  • hydrophilic monomers are understood as meaning polymerizable olefinically unsaturated compounds which are wholly or partly soluble in water (more than 2.5% by weight at 20 ° C.). Examples include: acrylic acid and its alkali and ammonium salts, methacrylic acid and its
  • Alkali and ammonium salts hydroxyethyl methacrylate, hydroxyethyl acrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, triethylene glycol monoacrylate, triethylene glycol monomethacrylate, tetraethylene glycol monoacrylate, tetraethylene glycol monomethacrylate, vinyl amide, methacrylamide, methacrylate, methacrylate, methacrylate, methacrylate Aminoethyl methacrylate, N, N-dimethylaminoethyl methacrylate, acrylamide, methacrylamide, vinyl pyrolidone and vinyl imidazole are preferred.
  • Particularly preferred polymer compounds are copolymers of
  • hydrophilic monomer from the group aminoethyl methacrylate, N, N-dimethylammoethyl methacrylate, acrylamide, methacrylamide, vinyl pyrolidone and vinyl imidazole.
  • Other highly suitable polymer compounds are those with built-in fluorine groups and perfluoroalkyl groups, for example homopolymers and copolymers of heptafluorobutyl methacrylate.
  • the amount of polymer compound is 0.1% by weight to 20% by weight, preferably 0.5% by weight to 7.5% by weight, based on the thermoplastic particles.
  • thermoplastic particles with polymer compounds can again be carried out in such a way that the untreated particles are treated with a solution of the
  • Polymer compound are brought into contact.
  • a non-aqueous is suitable
  • Solvents such as e.g. Isooctane or toluene.
  • the solvent can again be removed by evaporation, if appropriate at elevated temperature or using reduced pressure.
  • Trimethylchlorosilane, dimethyldichlorosilane, hexamethyldisiloxane, propyltrimethoxysilane, gammaaminopropyltrimethoxysilane and mixtures of these silanes are suitable for the treatment with silanes.
  • the treatment with silane can take place without a solvent or, which is particularly advantageous, in an aprotic solvent.
  • Suitable solvents are, for example, acetone, butanone, dichloromethane, trichloromethane, toluene, ethyl acetate or tetrahydrofuran.
  • a catalyst can of course be used in the silanization.
  • Protonic acids such as acetic acid or hydrogen chloride
  • amines such as dicyclohexylamine
  • the coating can also be carried out by first hydrolyzing the silane with acidic catalysis using, for example, molar amounts of water, the hydrolyzable radicals X being in OH groups are transferred, and then the freshly prepared OH compound is reacted with the thermoplastic particles in a solvent.
  • the amount of silane used can be varied to a large extent; it is usually in the range from 0.05 to 10% by weight, preferably 0.2 to 5% by weight, based on the thermoplastic particles.
  • thermoplastics according to the invention lead to rapid prototyping by laser sintering to models with improved surface quality, greater level of detail and increased contour accuracy.
  • the models obtained do not have to be reworked, or less so than the models of the current state of the art.
  • Thermoplastic particles that have not been used in one operation remain unchanged; in particular, no agglomerates form and they can be completely reused.
  • the contact angles of the samples modified according to the invention are significantly higher than those of the unmodified polyamide 12 and demonstrate the reduced wettability.
  • the surface quality of the sintered material was improved compared to the samples made from untreated polyamide.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Mechanical Engineering (AREA)

Abstract

L'invention concerne l'utilisation de poudres de plastiques thermodurcissables, à surface modifiée, dans le prototypage rapide. Le frittage sélectif au laser permet alors de réaliser des modèles améliorés en termes de qualité de surface, de degré de détail et de précision de contour.
PCT/EP2002/006138 2001-06-18 2002-06-04 Procede pour realiser des modeles tridimensionnels par frittage selectif au laser WO2002102576A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10129305.4 2001-06-18
DE10129305A DE10129305A1 (de) 2001-06-18 2001-06-18 Verfahren zur Herstellung von dreidimensionalen Mustern

Publications (1)

Publication Number Publication Date
WO2002102576A1 true WO2002102576A1 (fr) 2002-12-27

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PCT/EP2002/006138 WO2002102576A1 (fr) 2001-06-18 2002-06-04 Procede pour realiser des modeles tridimensionnels par frittage selectif au laser

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DE (1) DE10129305A1 (fr)
WO (1) WO2002102576A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017033146A1 (fr) * 2015-08-26 2017-03-02 Sabic Global Technologies B.V. Procédé de production de poudres de polycarbonates cristallins
CN107810215A (zh) * 2015-06-19 2018-03-16 斯特塔思有限公司 用于增材制造的水分散性聚合物
US10500763B2 (en) 2015-06-23 2019-12-10 Sabic Global Technologies B.V. Manufacturability of amorphous polymers in powder bed fusion processes

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10306886A1 (de) 2003-02-18 2004-09-02 Daimlerchrysler Ag Verfahren und Vorrichtung zur Herstellung von Körpern durch sequentiellen Materialschichtaufbau
US20050207931A1 (en) 2004-03-21 2005-09-22 Toyota Motorsport Gmbh unknown
WO2005090448A1 (fr) 2004-03-21 2005-09-29 Toyota Motorsport Gmbh Poudres pour prototypage rapide et procede de production correspondant
US9833788B2 (en) 2004-03-21 2017-12-05 Eos Gmbh Electro Optical Systems Powder for layerwise manufacturing of objects
WO2006056198A2 (fr) 2004-11-26 2006-06-01 Gn Resound A/S Procede d'apport d'un tube sonore a forme prefaçonnee
US8247492B2 (en) 2006-11-09 2012-08-21 Valspar Sourcing, Inc. Polyester powder compositions, methods and articles
WO2008057844A1 (fr) 2006-11-09 2008-05-15 Valspar Sourcing, Inc. Compositions de poudre et procédés de fabrication d'articles à partir de celles-ci
US9895842B2 (en) 2008-05-20 2018-02-20 Eos Gmbh Electro Optical Systems Selective sintering of structurally modified polymers
DE102010062875A1 (de) * 2010-12-13 2012-06-14 Bayerische Motoren Werke Aktiengesellschaft Verfahren zur Herstellung eines Bauteils durch Lasersintern
WO2022004418A1 (fr) * 2020-06-29 2022-01-06 東山フイルム株式会社 Feuille de dégagement

Citations (3)

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US5304329A (en) * 1992-11-23 1994-04-19 The B. F. Goodrich Company Method of recovering recyclable unsintered powder from the part bed of a selective laser-sintering machine
US5385780A (en) * 1990-12-05 1995-01-31 The B. F. Goodrich Company Sinterable mass of polymer powder having resistance to caking and method of preparing the mass
US6245281B1 (en) * 1997-10-27 2001-06-12 Huels Aktiengesellschaft Use of a nylon-12 for selective laser sintering

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
US5385780A (en) * 1990-12-05 1995-01-31 The B. F. Goodrich Company Sinterable mass of polymer powder having resistance to caking and method of preparing the mass
US5304329A (en) * 1992-11-23 1994-04-19 The B. F. Goodrich Company Method of recovering recyclable unsintered powder from the part bed of a selective laser-sintering machine
US6245281B1 (en) * 1997-10-27 2001-06-12 Huels Aktiengesellschaft Use of a nylon-12 for selective laser sintering

Non-Patent Citations (1)

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Title
KELLER, PETER: "Der Stoff, aus dem die Prototypen sind", KUNSTSTOFFE, vol. 89, no. 11, 1 November 1999 (1999-11-01), pages 58 - 61, XP002213140 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107810215A (zh) * 2015-06-19 2018-03-16 斯特塔思有限公司 用于增材制造的水分散性聚合物
CN107810215B (zh) * 2015-06-19 2020-08-07 斯特塔思有限公司 用于增材制造的水分散性聚合物
US10500763B2 (en) 2015-06-23 2019-12-10 Sabic Global Technologies B.V. Manufacturability of amorphous polymers in powder bed fusion processes
WO2017033146A1 (fr) * 2015-08-26 2017-03-02 Sabic Global Technologies B.V. Procédé de production de poudres de polycarbonates cristallins
US10597498B2 (en) 2015-08-26 2020-03-24 Sabic Global Technologies B.V. Method of producing crystalline polycarbonate powders

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