EP1085972A1 - Procede et materiau pour produire des corps-modeles - Google Patents

Procede et materiau pour produire des corps-modeles

Info

Publication number
EP1085972A1
EP1085972A1 EP99950332A EP99950332A EP1085972A1 EP 1085972 A1 EP1085972 A1 EP 1085972A1 EP 99950332 A EP99950332 A EP 99950332A EP 99950332 A EP99950332 A EP 99950332A EP 1085972 A1 EP1085972 A1 EP 1085972A1
Authority
EP
European Patent Office
Prior art keywords
methacrylate
acrylate
acid esters
decyl
butyl
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.)
Withdrawn
Application number
EP99950332A
Other languages
German (de)
English (en)
Inventor
Wolfgang Podszun
David Bryan Harrison
Gabriele Alscher
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.)
Bayer AG
Original Assignee
Bayer 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 Bayer AG filed Critical Bayer AG
Publication of EP1085972A1 publication Critical patent/EP1085972A1/fr
Withdrawn legal-status Critical Current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
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/003—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/141—Processes of additive manufacturing using only solid materials
    • B29C64/153—Processes of additive manufacturing using only solid materials using layers of powder being selectively joined, e.g. by selective laser sintering or melting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • 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
    • B29K2033/00—Use of polymers of unsaturated acids or derivatives thereof as moulding material
    • B29K2033/04—Polymers of esters

Definitions

  • the invention relates to a process for the production of model bodies, in which, using plastics, in the form of selected bead polymers, any three-dimensional structure can be built up using selective sintering using laser light.
  • the invention also relates to a special material that is particularly suitable for laser sintering.
  • the invention particularly relates to a method for producing three-dimensional
  • Rapid prototyping is the term used to summarize the computer-controlled, additive, automatic model building processes known today.
  • Laser sintering is a rapid prototyping process in which fillings made of certain powdery materials are heated and fused or sintered at certain points in the room under the influence of laser beams, preferably controlled by a program.
  • Low-melting metals are sintered in a process for the production of three-dimensional tools for the shaping of thermoplastic plastic using a rapid prototyping system.
  • Low-melting metals and / or metal alloys with a melting point below 200 ° C. are used in the form of metal powder or metal foils free from plastic binders or metallic binders.
  • the energy of the laser radiation used is set up in accordance with the melting point of the metals and / or metal alloys used. With this procedure none Models are created from plastics. It is also not possible to obtain metal models from high-melting metals.
  • the process serves both for the production of plastic models and for the production of positive preforms for ceramic casting molds.
  • a disadvantage of the known plastic powders is their poor flowability, which can only be partially reduced by the use of flow aids.
  • Polystyrene for the preform is feasible, but the surface quality of the preform is not fully satisfactory.
  • the polymer preform is then surrounded with ceramic material that is fired at high temperatures for solidification.
  • the polymer material is volatilized during this process. Complete volatilization is desired.
  • the object of the invention was to find a material suitable for the sintering process by means of lasers which has a smooth to fine-grained surface after
  • the invention relates to a method for producing three-dimensional
  • the weight average is given here.
  • Bead polymers with an average particle diameter of 5 to 100 ⁇ m are particularly suitable for the process according to the invention.
  • the bead polymers to be used according to the invention have much more favorable flow properties than ground other plastics and therefore do not require any flow aids to improve their flow properties.
  • the bead polymer does not leave any troublesome residues when it is incinerated, for example as the core of a hollow ceramic mold.
  • plastic models which are primarily created using laser sintering, are further processed in subsequent processes for investment casting.
  • the model is immersed in a slurried ceramic mass and the model coated with ceramic material is fired in the furnace.
  • the model should burn completely when fired and leave the free hollow shape made of ceramic. Since conventional ground plastics do not burn completely due to the flow aid, the metallic models subsequently cast in the ceramic mold often have surface inaccuracies.
  • the bead polymers for the purposes of the present invention are polymer particles which are largely spherical.
  • Different processes for the production of spherical particles are known, for example polymerization processes such as suspension or. Bead polymerization, dispersion polymerization, seed feed polymerization, further atomization techniques and precipitation processes. So bead polymers with a particle size of about 10 to 200 microns can be obtained by suspension polymerization or bead polymerization.
  • suspension polymerization is understood to mean a process in which a monomer or a monomer-containing mixture which contains an initiator soluble in the monomer (s) in a phase which is essentially immiscible with the monomer (s) and which contains a dispersant, in the form of droplets, optionally in a mixture with small, solid particles, and is cured by increasing the temperature with stirring. Further details of the suspension polymerization are published, for example, in the publication "Polymer Processes" CE Schildknecht, published in 1956 by Interscience Publishers, Inc. New York, described in the chapter “Polymerization in Suspension” on pages 69 to 109.
  • Bead polymers with a particle size of 2 to 10 ⁇ m can be produced by the so-called dispersion polymerization.
  • a suitable method is described, for example, in EP-A-610 522.
  • Dispersion polymerization uses a solvent in which the monomers used are soluble but the polymer formed is insoluble.
  • Dispersion polymerization generally provides bead polymers with a narrow particle size distribution.
  • the bead polymers to be used according to the invention preferably consist of homopolymers or copolymers of monoethylenically unsaturated compounds (monomers).
  • copolymers are understood to be polymers which are composed of two or more different monomers. Suitable monomers are e.g. Styrene, alpha-methylstyrene, chlorostyrene,
  • Acrylic acid esters such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, dodecyl acrylate, methacrylic acid esters, such as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, hexyl methacrylate, 2-ethyl decyl methyl acrylate, methacrylate methacrylate, Methacrylonitrile, methacrylamide and vinyl acetate.
  • methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, hexyl methacrylate, 2-ethyl decyl methyl acrylate, methacrylate methacryl
  • homo- and copolymers of methacrylic acid esters and / or acrylic acid esters are particularly preferred.
  • Polymethyl methacrylate and copolymers with a proportion of more than 60% by weight of methyl methacrylate units are particularly preferred.
  • Well-suited copolymers are, for example, those which are 60 to 98
  • % By weight of methyl methacrylate units and 2 to 40% by weight of units of acrylic acid esters and / or methacrylic acid esters having 4 to 18 carbon atoms in the alcohol part, in particular copolymers of methyl methacrylate with one or more monomers from the group: n-butyl acrylate, iso- Butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, dodecyl acrylate, n-butyl methacrylate, iso-butyl methacrylate acrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, dodecyl methacrylate, stearyl methacrylate.
  • the molecular weight of the bead polymers can be important for the suitability for the process according to the invention.
  • the molecular weight should in particular be from 10,000 to 1,000,000, preferably from 10,000 to 500,000, particularly preferably from 20,000 to 250,000 g / mol.
  • molecular weight regulators can be used in the preparation of the bead polymers. Suitable molecular weight regulators are especially sulfur compounds, e.g. n-butyl mercaptan, dodecyl mercaptan, ethyl thioglycolate and diisopropyl xanthogen disulfide.
  • the sulfur-free regulators mentioned in DE 3 010 373 are also very suitable for adjusting the molecular weight, for example the enol ethers of the formula I.
  • Suitable laser types are all that bring the bead polymer to sintering, fusing or crosslinking, in particular CO2 laser (10 ⁇ m) ND-YAG laser (1,060 nm) He-Ne laser (633 nm) or dye laser (350-1,000 nm). A CO 2 laser is used before.
  • the energy density in the bed is preferably from 0.1 to 10 J / mm 3 during irradiation.
  • the effective diameter of the laser beam is preferably from 0.01 to 0.5 nm, preferably 0.1 to 0.5 nm, depending on the application.
  • Pulsed lasers are preferably used, a high pulse frequency, in particular from 1 to 100 kHz, having proven particularly suitable.
  • the preferred procedure can be described as follows:
  • the laser beam strikes the uppermost layer of the bed of the material to be used according to the invention and sinters the material in a certain layer thickness.
  • This layer thickness can be from 0.01 mm to 1 mm, preferably from 0.05 to 0.5 mm.
  • the working space is then lowered by an amount which is less than the thickness of the sintered layer.
  • the work space is filled up to the original height with additional polymer material.
  • the second layer of the component is sintered and connected to the previous layer. By repeating the process, the additional layers are created until the component is finished.
  • the exposure speed when scanning the laser is preferably 1 to 1,000 mm / s. Typically a speed of about 100 mm / s is used.
  • the invention also relates to the models obtainable by the process according to the invention.
  • Another object of the invention is the use of the models which are produced by the method according to the invention for the production of preforms, in particular of ceramic, for the investment casting of metals.
  • Figure 1 shows the simplified schematic representation of a rapid prototyping
  • Examples 1 to 6 below show the production of suitable fine-particle plastic material for laser sintering.
  • the rapid prototyping system used to manufacture the models has the following basic structure (FIG. 1).
  • the beam from an IR laser 1 is directed via a deflecting mirror 2 according to the specification of a scanner unit (not shown) onto the surface of the bed 4 of a bead polymer, which is held in a round shape 5 with a movable lower punch 6.
  • Layers 3a, 3b of sintered plastic material are formed by the exposure. After each exposure and generation of a layer (e.g. 3b), the
  • Stamp 6 lowered by a layer thickness and the bed 4 supplemented with new plastic material, which is exposed in the next step, whereby the next layer 3 a of the model body is generated.
  • Bead polymer was isolated by centrifugation, washed with methanol and dried at 50 ° C. 780 g of a bead polymer with an average particle size of 5.3 ⁇ m were obtained.
  • the average molecular weight M w was 110,000 g / mol.
  • Enol ethers according to formula I were mixed to form a homogeneous solution.
  • the solution was transferred to a stirred reactor which had previously been treated with 1.5 liters of a 1% strength by weight aqueous alkaline solution of a copolymer of 50% by weight methacrylic acid and 50% by weight adjusted to pH 8 with sodium hydroxide solution .-% methyl methacrylate had been filled.
  • the stirring speed was set at 420 revolutions per minute.
  • the temperature was held at 78 ° C for 8 hours and then at 85 ° C for 1 hour.
  • the mixture was then cooled to room temperature, the bead polymer obtained was isolated by decanting, washed several times with water and dried at 60.degree. 465 g of a bead polymer with an average particle size of 45 ⁇ m were obtained.
  • the temperature was held at 55 ° C for one hour, then at 75 ° C for 12 hours and then at 90 ° C for 4 hours.
  • the mixture was then cooled to room temperature, the bead polymer obtained was isolated by filtration through a 32 ⁇ m filter cloth, washed several times with water and dried at 35 ° C. under 20 mbar vacuum. After sieving through a 125 ⁇ m sieve, a bead polymer with a Staudinger index, [ ⁇ ], (Ubbelohde capillary viscometer in chloroform at 25 ° C.) of 1.01 dl / g was obtained, which had a molecular weight M w of 250,000 g / Mol corresponds.
  • the flowability of some polymers was quantified by means of determination of the angle of repose and determination of the flow angle.
  • the angle of repose is here
  • the cone is created by discharging the bulk material from a funnel with a narrow outlet onto a flat surface.
  • the flow angle is the angle that an inclined surface makes in relation to the horizontal, and at which bulk material spread over the surface begins to flow under the influence of gravity.
  • the plastic powder is sintered in a model system.
  • the plastic powder is exposed in layers at a speed of 1 mm s under an infrared laser with a wavelength of 10,000 nm (CO 2 laser) at a maximum temperature of 500 ° C.
  • the plastic powders tested from Examples 7 and 8 were sintered.

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

L'invention concerne un procédé permettant de produire des corps-modèles, selon lequel on peut obtenir, à l'aide de matières plastiques, notamment de polymérisats en perles sélectionnés, n'importe quel type de structure tridimensionnelle, par agglomération sélective à l'aide de lumière laser. L'invention concerne en outre un matériau spécial convenant particulièrement à l'agglomération par laser. La matière plastique pulvérulente utilisée est un polymérisat en perles, à base d'homo- ou de copolymérisat de composés insaturés monoéthyléniquement, de diamètre particulaire moyen compris entre 2 et 200 °m.
EP99950332A 1998-05-11 1999-05-06 Procede et materiau pour produire des corps-modeles Withdrawn EP1085972A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19820725A DE19820725A1 (de) 1998-05-11 1998-05-11 Verfahren und Material zur Herstellung von Modellkörpern
DE19820725 1998-05-11
PCT/EP1999/003131 WO1999058317A1 (fr) 1998-05-11 1999-05-06 Procede et materiau pour produire des corps-modeles

Publications (1)

Publication Number Publication Date
EP1085972A1 true EP1085972A1 (fr) 2001-03-28

Family

ID=7867167

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99950332A Withdrawn EP1085972A1 (fr) 1998-05-11 1999-05-06 Procede et materiau pour produire des corps-modeles

Country Status (8)

Country Link
EP (1) EP1085972A1 (fr)
JP (1) JP2002514527A (fr)
AU (1) AU4258799A (fr)
BR (1) BR9910364A (fr)
CA (1) CA2331528A1 (fr)
DE (1) DE19820725A1 (fr)
TW (1) TW453947B (fr)
WO (1) WO1999058317A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004012683A1 (de) * 2004-03-16 2005-10-06 Degussa Ag Lasersintern mit Lasern mit einer Wellenlänge von 100 bis 3000 nm
DE102015016959A1 (de) 2015-12-24 2016-06-09 Daimler Ag Verfahren zum Herstellen eines Bauteils und Kraftfahrzeug mit einem solchen Bauteil
DE102018108001A1 (de) 2018-04-05 2019-10-10 Lean Plastics Technologies GmbH Verfahren und Vorrichtung zur Herstellung von kugelförmigen Polymerpartikeln und deren Verwendung
DE102019109005A1 (de) * 2019-04-05 2020-10-08 Lean Plastics Technologies GmbH Verfahren und Vorrichtung zur Herstellung von Kunststoffpartikeln

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5733497A (en) * 1995-03-31 1998-03-31 Dtm Corporation Selective laser sintering with composite plastic material
US5817206A (en) * 1996-02-07 1998-10-06 Dtm Corporation Selective laser sintering of polymer powder of controlled particle size distribution

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9958317A1 *

Also Published As

Publication number Publication date
CA2331528A1 (fr) 1999-11-18
BR9910364A (pt) 2001-02-06
DE19820725A1 (de) 1999-11-18
AU4258799A (en) 1999-11-29
JP2002514527A (ja) 2002-05-21
WO1999058317A1 (fr) 1999-11-18
TW453947B (en) 2001-09-11

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