WO2015105762A1 - Matériaux et procédés de fabrication tridimensionnelle - Google Patents

Matériaux et procédés de fabrication tridimensionnelle Download PDF

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Publication number
WO2015105762A1
WO2015105762A1 PCT/US2015/010231 US2015010231W WO2015105762A1 WO 2015105762 A1 WO2015105762 A1 WO 2015105762A1 US 2015010231 W US2015010231 W US 2015010231W WO 2015105762 A1 WO2015105762 A1 WO 2015105762A1
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WO
WIPO (PCT)
Prior art keywords
precursor
build region
carrier
region
sheet
Prior art date
Application number
PCT/US2015/010231
Other languages
English (en)
Inventor
Edward T. Samulski
Joseph M. Desimone
Original Assignee
Carbon3D, Inc.
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 Carbon3D, Inc. filed Critical Carbon3D, Inc.
Publication of WO2015105762A1 publication Critical patent/WO2015105762A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/165—Processes of additive manufacturing using a combination of solid and fluid materials, e.g. a powder selectively bound by a liquid binder, catalyst, inhibitor or energy absorber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/30—Auxiliary operations or equipment
    • B29C64/307—Handling of material to be used in additive manufacturing
    • B29C64/321—Feeding

Definitions

  • the present invention concerns methods, compositions and apparatus for forming three-dimensional objects from thermoset resins.
  • SLS selective laser sintering
  • a laser for example, a carbon dioxide laser
  • the laser selectively fuses powdered material by scanning cross -sections generated from a 3-D digital description of the part (for example from a CAD file or scan data) onto the surface of a powder bed. After each cross-section is scanned, the powder bed is lowered by one layer thickness, a new layer of material is applied to the top surface thereof, and the process is repeated until the part is completed. Because finished part density depends on peak laser power rather than laser duration, a SLS machine typically uses a pulsed laser.
  • the SLS machine may preheat the bulk powder material in the powder bed to a point below its melting point, to make it easier for the laser to raise the temperature of the selected regions the rest of the way to the melting point.
  • SLA stereolithography
  • FDM fused deposition modeling
  • SLS does not require extensive support structures because the part being constructed is surrounded by unsintered powder at all times. Hence, parts can be made that may be difficult to achieve by other techniques.
  • the materials available for use in SLS have heretofore been limited, and there is a need for new materials which can be used in SLS-type processes.
  • a first aspect of the present invention is a process for the production of a three- dimensional object from a high performance polymer, comprising the steps of;
  • the cross-linking step is a thermally cross-linking step (e.g., with a carbon dioxide laser as the radiation source), and said precursor is optionally but preferably in solid form (e.g., as a powder or sheet);
  • the cross-linking step is a photo -polymerization step, and said precursor is optionally but preferably in liquid form (e.g., as a melt; as a solution with a solvent such as low molar mass free radically polymerizable monomers; or as a combination thereof).
  • the high performance polymer comprises a liquid crystalline thermos et (LCT) such as an ester, ester-imide, or ester-amide oligomer.
  • LCT liquid crystalline thermos et
  • the precursor has at least one reactive alkene-containing or alkyne-containing end-cap covalently coupled thereto (e.g., a phenylacetylene, phenylmaleimide, or nadimide end-cap).
  • a reactive alkene-containing or alkyne-containing end-cap covalently coupled thereto (e.g., a phenylacetylene, phenylmaleimide, or nadimide end-cap).
  • the precursor is provided to said build region in solid form (e.g., as a particulate); in other embodiments, the precursor oligomer is provided to the build region in the form of a continuous solid sheet or sections of a solid sheet.
  • the cross-linking step is carried out by laser irradiation.
  • the cross-linking step is carried out with patterned irradiation.
  • the cross-linking step is a heating step is carried out by laser sintering.
  • a further aspect of the invention is an apparatus for forming a three-dimensional object of a high-performance polymer, comprising:
  • an energy source e.g., a heat or actinic radiation source source, such as a carbon dioxide laser
  • a sheet supply assembly operatively associated with said carrier and configured to advance a precursor of the high performance polymer into said build region as a solid sheet (e.g., continuously or in segments).
  • the apparatus further comprises (d) a surplus sheet take-up assembly operatively associated with said sheet supply assembly and configured to advance unused precursor of the high performance polymer out of said build region as a solid sheet.
  • the apparatus further comprises a controller operatively associated with said carrier, said radiation source, said sheet supply assembly, and optionally said surplus sheet take-up assembly, the controller configured to advance the carrier away from the build region, and advance new solid sheet precursor into said build region.
  • the sheet supply assembly comprises a roller, chain drive, conveyor belt, or vacuum transfer assembly, or a combination thereof.
  • the surplus sheet take-up assembly comprises a roller, chain drive, conveyor belt, vacuum transfer assembly, or combination thereof (separate from or together with said sheet supply assembly).
  • the energy source comprises a patterned energy source.
  • the energy source comprises a laser (e.g. a carbon dioxide laser).
  • Figure 1 is a schematic illustration of an apparatus useful for carrying out the present invention.
  • the device may otherwise be oriented (rotated 90 degrees or at other orientations) and the spatially relative descriptors used herein interpreted accordingly.
  • the terms “upwardly,” “downwardly,” “vertical,” “horizontal” and the like are used herein for the purpose of explanation only, unless specifically indicated otherwise.
  • first, second, etc. may be used herein to describe various elements, components, regions, layers and/or sections, these elements, components, regions, layers and/or sections should not be limited by these terms. Rather, these terms are only used to distinguish one element, component, region, layer and/or section, from another element, component, region, layer and/or section. Thus, a first element, component, region, layer or section discussed herein could be termed a second element, component, region, layer or section without departing from the teachings of the present invention.
  • the sequence of operations (or steps) is not limited to the order presented in the claims or figures unless specifically indicated otherwise.
  • high performance polymers resins are used as the polymerizable precursor.
  • Numerous examples of such high performance polymers are known, including but not limited to those described in Narang and Fuller, US Patent No. 7,517,641 (Xerox).
  • suitable precursors resins include, but are not limited to, resins for those materials sometimes referred to as liquid crystalline polymers of esters, ester-imide, and ester-amide oligomers, as described in US Patents Nos. 7,507,784; and 6,939,940.
  • the LCT end-caps are selected for ease of thermosetting for 3D printing via laser sintering, as discussed below, or other processes that will be apparent in view of the present disclosure.
  • Liquid crystal thermoset monomers (“LCT monomers”) or LCT oligomers as used herein may refer to liquid crystal monomers or liquid crystal oligomers that form a liquid crystal thermoset when polymerized (e.g. by chain-extension and/or by cross-linking).
  • the LCT monomers or oligomers can thus be regarded as a macro-monomer or an oligomer of a liquid crystal thermoset.
  • Olemer(s) refers to mixtures of varying backbone length liquid crystal polymers, preferably of maximally 500 repeat units, within the weight range of approximately 500 to approximately 15,000 grams per mole, and which in some embodiments are not isolated as discreet molecular weight molecules.
  • LCT oligomers are relatively short linear liquid crystal polymers (LCPs). LCPs exhibit higher degrees of molecular order (chain parallelism) while in the molten state than other polymeric species.
  • LCT oligomers preferably comprise a liquid crystal backbone selected from the group consisting of an ester, an ester-imide and an ester-amide, wherein the backbone of the oligomer is entirely, or at least substantially entirely, aromatic in composition. This means that preferably at least 95 mol%, more preferably at least 99 mol%, even more preferably 100 mol% of the monomers present in the backbone are aromatic.
  • LCT oligomers are known and described in US Patents Nos. 7,507,784 and 6,939,940 toumblemans et al., the disclosures of which are incorporated by reference herein in their entirety.
  • the LCT oligomer may be capable of polymerizing by chain-extension.
  • the liquid crystal oligomers are preferably end-capped with self-reactive end-groups, in which case the LCT oligomer has a general structure of: wherein:
  • Z indicates the oligomer backbone (e.g., an LCT oligomer as described above and below); and each E is an independently selected end-cap, such as an alkene or alkyne end- cap (as discussed further below).
  • Such a reactive or self-reactive end-cap is capable of reacting with another self- reactive end-cap of the same type and (optionally) to some extent with the HPP it is intended to reinforce. Accordingly, an LCT oligomer with reactive end-caps is capable of chain- extension.
  • the end-cap is preferably a vinyl, acetylene, or diacetylene- containing group such as a phenylacetylene, phenylmaleimide, or nadimide end-cap, examples of which include but are not limited to;
  • the LCT oligomers may have a backbone having at least one structural repeat unit selected from the group consisting of
  • Ar is an aromatic group.
  • Ar may in particular be an aromatic group selected from;
  • X is selected from the group consisting of
  • n is a number or integer less than 500
  • E and E' are selected from the group consisting of:
  • R' is selected from the group consisting of hydrogen, alkyl groups containing six or less carbon atoms, aryl groups containing six or less carbon atoms, aryl groups containing less than ten carbon atoms, lower alkoxy groups containing six or less carbons, lower aryloxy groups containing ten or less carbon atoms, fluorine, chlorine, bromine and iodine.
  • X -COOH or -OH or -NH 2 where each group Ar may, in the alternative to being phenyl as shown, be any aromatic or aryl group. It will be appreciated that group X forms a linking group to the oligomer backbone "Z" when reacted thereto.
  • the arylethynyl benzoic acid end-cap is a useful one to claim for 3D print applications.
  • the arylethynyl and norbornene functionality are used for the thermal post polymerization step and the -COOH, -OH or -NH2 functionality are needed to end-cap the oligomer chain. Note also that any meta- or para-substituted one or multiple aromatic ring system may be used.
  • any suitable free-radically polymerizable material can be used in combination with the above LCP resins to provide composites useful for carrying out the present invention.
  • suitable free-radically polymerizable material examples include, but are not limited to, acrylics, methacrylics, acrylamides, styrenics, olefins, halogenated olefins, cyclic alkenes, maleic anhydride, alkenes, alkynes, carbon monoxide, functionalized oligomers, multifunctional cure site monomers, etc., including combinations thereof.
  • liquid resins, monomers and initiators include but are not limited to those set forth in US Patents Nos. 8,232,043; 8,119,214; 7,935,476; 7,767,728; 7,649,029; WO 2012129968 Al; CN 102715751 A; JP 2012210408 A.
  • the resin or polymerizable precursor material can have solid particles suspended or dispersed therein. Any suitable solid particle can be used, depending upon the end product being fabricated.
  • the particles can be metallic, organic/polymeric, inorganic, or composites or mixtures thereof.
  • the particles can be of any suitable shape, including spherical, elliptical, cylindrical, fractal, etc.
  • the particles can comprise an active agent or detectable compound as described below. For example, magnetic or paramagnetic particles or nanoparticles can be employed.
  • the resin can have have additional ingredients solubilized, dispersed or suspended therein, including pigments, dyes, active compounds or pharmaceutical compounds, detectable compounds ⁇ e.g., fluorescent, phosphorescent, radioactive), etc., again depending upon the particular purpose of the product being fabricated,
  • the LCT oligomers are cured, thereby irreversibly forming a covalently-linked polymer network, In this process, at least some of the reactive LCT oligomers are cross-linked. Cross-linking occurs in particular between the reactive termini of the aromatic backbones of the LCT oligomers. Initiating polymerization (chain extension/crosslinking) as used herein may therefore particularly refer to initiating cross-linking of the LCT oligomers, and in particular to initiating cross-linking of the backbone of the LCT oligomers.
  • One embodiment of the invention provides the precursor to the build region in solid particulate form, which may then be irradiated, and fresh particulate precursor provided to the build region, in like manner as employed for other materials in laser sintering. See, e.g., US Patents Nos. 6,858,816; 5,525,264; and 5,155,321, This embodiment takes advantage of the inherent physical properties of the LCT precursor resin.
  • LCT is a "macromonomer”— a low molecular weight, typically crystalline organic compound, it is crystalline or glassy and consequently very brittle. This brittleness lends itself to ease of grinding into a free-flowing, micron or smaller sized powder, which is ideally suited for selective laser sintering (SLS) 3D printing.
  • FIG. 1 Another embodiment of a method and apparatus of the invention is schematically illustrated in Figure 1.
  • a thin (1 to several hundred micron thick) film or sheet (11) of the oligomer (the high performance polymer precursor in solid form) is fed (from the right) by a roller supply assembly (12) into a "build region" defined by a carrier (13) and light or energy source (14) ⁇ e.g., a laser such as a carbon dioxide laser).
  • a fresh section of film is translated and held on top surface of the object being produced (15), or the "build" (center object below film).
  • the film is fused e.g., by laser beam (dotted arrows above film and build object) into 2D pattern completing a layer of "build” on the lowering carrier (or build plate), The first layer of build is translated downwards.
  • Another "fresh" section of film is translated into the build region (in the illustrated embodiment from right-to-left), and the foregoing steps are repeated until the fabrication of the object or article is completed. Wasted sheet material (unfused area of film) is collected by the roller take-up assembly (16) at left and recycled.
  • a controller and associated drives and patterning elements for patterning the light or thermal energy may be provided in accordance with known techniques.
  • both the sheet supply assembly and the surplus sheet take-up assembly may comprise a roller, chain drive, conveyor belt, or vacuum transfer assembly, or a combination thereof.
  • the precursors described herein may be used in liquid form for photo-polymerization as the polymerizable liquid in a "bottom up” or “top down” three-dimensional printing (or additive manufacturing) method and apparatus, including but not limited to those set forth in US Patent No. 5,236,637 to Hull.

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

Abstract

L'invention porte sur un procédé qui permet de produire un objet tridimensionnel constitué d'un polymère de haut rendement (par exemple un polymère thermodurcissable à cristaux liquides), et qui est exécuté par (a) l'utilisation d'une source de rayonnement (par exemple un laser au dioxyde de carbone) et d'un support pour le support d'un objet tridimensionnel pendant sa fabrication, la source de rayonnement et le support délimitant une région de construction ; (b) l'apport d'un précurseur d'un polymère de haut rendement à la région de construction sous forme liquide ou solide ; (c) la réticulation (par exemple la réticulation thermique) du précurseur dans la région de construction afin de produire une région polymérisée solide du polymère ; (d) l'avance dudit support sur lequel ladite région polymérisée a adhéré pour l'éloigner de ladite région de construction afin de créer une région de construction subséquente entre la région polymérisée et ladite source de rayonnement ; (e) la répétition des étapes (b) à (d) jusqu'à ce que la fabrication de l'objet tridimensionnel soit terminée.
PCT/US2015/010231 2014-01-08 2015-01-06 Matériaux et procédés de fabrication tridimensionnelle WO2015105762A1 (fr)

Applications Claiming Priority (2)

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US201461924873P 2014-01-08 2014-01-08
US61/924,873 2014-01-08

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018106531A1 (fr) 2016-12-05 2018-06-14 Arkema Inc. Mélanges d'initiateurs et compositions photodurcissables contenant de tels mélanges d'initiateurs utiles pour l'impression 3d
WO2018144219A1 (fr) * 2017-02-02 2018-08-09 General Electric Company Procédé et appareil d'application de matière par couches pour la fabrication d'additif
WO2019094902A1 (fr) * 2017-11-13 2019-05-16 General Electric Company Fabrication additive à grande échelle de lits fixes à l'aide de matériaux de construction à base de feuilles
US10350573B2 (en) 2016-04-29 2019-07-16 Saint-Gobain Performance Plastics Corporation Radiation curable system and method for making a radiation curable article
US10688737B2 (en) 2017-09-14 2020-06-23 General Electric Company Method for forming fiber-reinforced polymer components
US11267944B2 (en) 2015-12-30 2022-03-08 Saint-Gobain Performance Plastics Corporation Radiation curable article and method for making and using same
WO2022055904A1 (fr) * 2020-09-10 2022-03-17 Mighty Buildings, Inc. Système d'obtention d'un prépolymère photopolymérisé
US11292187B2 (en) 2016-05-31 2022-04-05 Northwestern University Method for the fabrication of three-dimensional objects and apparatus for same
US11891465B2 (en) 2019-04-29 2024-02-06 Mighty Buildings, Inc. System for obtaining a photopolymerized prepolymer

Citations (4)

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US20040096585A1 (en) * 2000-09-29 2004-05-20 Claude Bonnebat Method and device for continuously coating at least a metal strip surface with a single-layer or multilayer crosslinkable polymer fluid film
US20090130449A1 (en) * 2007-10-26 2009-05-21 Envisiontec Gmbh Process and freeform fabrication system for producing a three-dimensional object
US20090288601A1 (en) * 2000-10-17 2009-11-26 Nanogram Corporation Coating formation by reactive deposition
US20120247652A1 (en) * 2009-12-24 2012-10-04 Fujikura Rubber Ltd. Prepreg winding method and apparatus

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040096585A1 (en) * 2000-09-29 2004-05-20 Claude Bonnebat Method and device for continuously coating at least a metal strip surface with a single-layer or multilayer crosslinkable polymer fluid film
US20090288601A1 (en) * 2000-10-17 2009-11-26 Nanogram Corporation Coating formation by reactive deposition
US20090130449A1 (en) * 2007-10-26 2009-05-21 Envisiontec Gmbh Process and freeform fabrication system for producing a three-dimensional object
US20120247652A1 (en) * 2009-12-24 2012-10-04 Fujikura Rubber Ltd. Prepreg winding method and apparatus

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11267944B2 (en) 2015-12-30 2022-03-08 Saint-Gobain Performance Plastics Corporation Radiation curable article and method for making and using same
US10350573B2 (en) 2016-04-29 2019-07-16 Saint-Gobain Performance Plastics Corporation Radiation curable system and method for making a radiation curable article
US11292187B2 (en) 2016-05-31 2022-04-05 Northwestern University Method for the fabrication of three-dimensional objects and apparatus for same
US11465339B2 (en) 2016-05-31 2022-10-11 Northwestern University Method for the fabrication of three-dimensional objects and apparatus for same
WO2018106531A1 (fr) 2016-12-05 2018-06-14 Arkema Inc. Mélanges d'initiateurs et compositions photodurcissables contenant de tels mélanges d'initiateurs utiles pour l'impression 3d
WO2018144219A1 (fr) * 2017-02-02 2018-08-09 General Electric Company Procédé et appareil d'application de matière par couches pour la fabrication d'additif
US10688737B2 (en) 2017-09-14 2020-06-23 General Electric Company Method for forming fiber-reinforced polymer components
WO2019094902A1 (fr) * 2017-11-13 2019-05-16 General Electric Company Fabrication additive à grande échelle de lits fixes à l'aide de matériaux de construction à base de feuilles
US10894299B2 (en) 2017-11-13 2021-01-19 General Electric Company Fixed bed large scale additive manufacturing using foil-based build materials
US11891465B2 (en) 2019-04-29 2024-02-06 Mighty Buildings, Inc. System for obtaining a photopolymerized prepolymer
WO2022055904A1 (fr) * 2020-09-10 2022-03-17 Mighty Buildings, Inc. Système d'obtention d'un prépolymère photopolymérisé

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