• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to a filament (1) for 3D printing, characterized in that it has a core (10) having a first composition and an envelope (11) surrounding the core (10) having a second composition different from that of the core (10), the core and the shell each comprising a thermoplastic material, the thermoplastic material of the shell being miscible with that of the core.
    公开号:FR3052386A1
    申请号:FR1655289
    申请日:2016-06-09
    公开日:2017-12-15
    发明作者:Perrine Legrand
    申请人:Corextrusion Group；
    IPC主号:
    专利说明:

    FILAMENT FOR 3D PRINTING, METHOD FOR MANUFACTURING SUCH FILAMENT, AND METHOD FOR MANUFACTURING OBJECT BY 3D PRINTING
    FIELD OF THE INVENTION
    The present invention relates to a filament for 3D printing, a method of manufacturing such a filament, and a method of manufacturing an object by 3D printing using such a filament.
    BACKGROUND OF THE INVENTION
    The manufacture of objects by 3D printing is becoming increasingly important, not only for prototyping but for industrial scale production.
    3D printing is understood to mean a process in which a filament of a thermoplastic material is driven through a supply tube to a printing head comprising heating means for heating the filament in a localized way. melts it, and then extrudes the molten material through a nozzle located downstream of the heating means in the path of the filament. The molten material is deposited on a support, in the form of successive superimposed layers.
    The first objects were made with ABS (acrylonitrile butadiene styrene) or PLA (polylactic acid) filaments, since this material is easily suitable for 3D printing. However, ABS does not give the object interesting mechanical properties; moreover, its fusion generates toxic vapors. Moreover, PLA, which has the advantage of being a biobased material, provides very low mechanical properties and degrades as it ages.
    The need has therefore appeared to manufacture objects by 3D printing having mechanical properties as close as possible to those obtained with traditional manufacturing processes such as the injection of thermoplastic materials, for example. For this purpose, attempts have been made to incorporate into the material a filler intended to modify the mechanical properties of the final object. These fillers may be in the form of powders, cut fibers or continuous or discontinuous fibers.
    However, the presence of these charges in the filament poses problems in the implementation of the 3D printing process.
    Thus, for example, in the case of a load consisting of glass fibers, which are abrasive, it has been found that the components of the 3D printer in contact with the filament (drive rollers, feed tube, etc.) wear out quickly.
    According to another example, in the case of a cliarge consisting of metallic particles, which are thermally conductive, it has been found that, in the print head, the filament is melted under the action of the heating means but that, by a thermal conduction effect by the metal fibers, a portion of the filament located upstream of the melted zone also heats, softens and sticks to the walls of the feed tube, thereby plugging said tube.
    Another problem with the use of technical materials such as polyamide is that since this material is subject to significant moisture uptake, the filament absorbs a significant amount of water prior to use. When the material is heated in the print head, the absorbed water turns into vapor and bubbles are created during printing, thus generating the object's beginnings.
    BRIEF DESCRIPTION OF THE INVENTION
    An object of the invention is therefore to design a filament for 3D printing that allows to overcome the aforementioned problems, while allowing to obtain bbjete having various mechanical properties, adapted to the intended use for the object .
    According to the invention, there is provided a filament for 3D printing, characterized in that it has a core having a first composition and an envelope surrounding the core having a second composition di ^ of that of the soul, l core and the envelope each comprising a thermoplastic material, the thermoplastic material of the envelope being miscible with that of the core.
    According to one embodiment, the core comprises a filler in the form of fibers or a powder and the envelope is devoid of a load.
    According to one embodiment, the load of the core comprises fibers of glass, carbon, poly (p-phenylene-2,6-benzobisoxaole) (PBO) and / or aramid.
    Advantageously, the fibers are chopped or ground fibers having a diameter of between 18 and 70 μm and a length of between 50 and 500 μm.
    According to one embodiment, the ream load comprises a powder of thermally conductive particles.
    Advantageously, the thermally concordant particles comprise metal particles.
    According to one embodiment, the core comprises polyamide and the envelope is made of a material impermeable to moisture and / or having a moisture recovery ture lower than that of the polyamide of the core.
    Advantageously, the core comprises PA6, PA6 / 66 or PA6 / 66/12.
    The shell material preferably comprises polyamide 12, polyamide 10 or polyamide 1010.
    Preferably, the envelope has a thickness of between 0.05 and 0.30 mm, preferably between 0.05 and 0.20 mm.
    The diameter of the fiiament is typically between 1 and 3 mm.
    Another object relates to a method of manufacturing the filament described above.
    According to said method, the envelope is formed around the core by coextrusion. The invention also relates to a method of manufacturing an object by 3D printing, in which a connection as described above is used. The invention also relates to a method for limiting the withdrawal of a manufactured object by 3D printing by means of a load contained in a filament, in which a filament as described above is provided, in which the core comprises a charge in the form of fibers or a powder and the envelope is devoid of a load, said fiiament is driven to a printing head in which said fiiament is heated locally, and the molten filament is extruded through a nozzle of a 3D printer so as to form the object by superposition of successive layers, the envelope preserving the components of the 3D printer wear by the load of the soul. The invention also relates to a method for controlling the softening of a filament comprising a charge of thermally conductive fibers during the manufacture of an object by 3D printing, in which a filament as described above is provided, wherein the core load comprises a powder of thermally conductive particles, in particular metal particles, said filament is driven to a printing head in which said filament is heated locally, and the molten filament is extruded through a nozzle of a printer 3D so as to form the object by superposition of successive layers, the envelope forming a thermally insulating barrier limiting the softening of the filament upstream of the area of the print head where it is heated. The invention finally relates to a method for preventing the formation of bubbles during the manufacture of an object by 3D printing with a filament comprising polyamide, in which a filament as described above is used, in which the envelope is made of a material impervious to moisture and / or having a moisture recovery rate lower than that of the polyamide of the core, the envelope thus forming a barrier to moisture absorption by the filament.
    BRIEF DESCRIPTION OF THE DRAWINGS Other characteristics and advantages of the invention will emerge from the detailed description which follows, with reference to the appended drawings in which; Figure 1 is a block diagram of a 3D printer, Figure 2 is a view of a filament according to one embodiment of the invention.
    For reasons of legibility of the figures, the different elements are not necessarily represented on the scale.
    DETAILED DESCRIPTION OF THE INVENTION
    Figure 1 is a block diagram of a 3D printer. The structure of such a printer is known in itself, only the components useful for understanding the invention are described here. The printer 100 is powered by a coil of a filament 1.
    Said filament 1 is introduced into the printer then driven and guided to a printing head 101 which comprises, from upstream to downstream on the path of the filament, a so-called "cold" zone 1010, a so-called "hot" zone 1011 comprising filament heating means adapted to melt locally, and a nozzle 1012 through which the molten material is extruded.
    A support 200 is placed facing the nozzle 1012 to receive the molten material and support the object during its manufacture by stacking layers.
    The cold zone 1010 is maintained at a temperature substantially lower than that of the hot zone so as not to cause melting of the filament in said zone 1010. Indeed, a melting or even a significant softening of the filament would cause clogging of the head. For this purpose, the cold zone may comprise cooling means.
    On its way to the head 101, the filament is driven by drive means 102 such as rollers for example. Before entering the head 101, the filament is guided in a tube 103.
    Naturally, the structure shown in Figure 1 is given by way of illustration and is in no way limiting with respect to the structure of 3D printers capable of using the filament according to the invention.
    Various embodiments of the filament will now be described.
    By "composition" we mean all the constituents of the soul and the envelope. These constituents comprise: at least one thermoplastic material (or a mixture of thermoplastic materials) forming a matrix having a melting point suitable for melting in a printing head of a 3D printer and then extruding through a nozzle at the outlet of the head, and optionally a charge in the form of particles (beads, fibers, etc.) and / or additives (for example: compatibilizing agents, softeners, colorants, etc.) making it possible to adjust the properties of the composition. The core and shell have thermoplastic materials that are miscible with each other, so that although the shell forms a separate layer of the core when the filament is introduced into the 3D printer, the material of the manufactured object is an intimate mixture of said materials.
    The compositions of the core and the shell may differ in the nature of their constituents and / or in the proportion of each constituent.
    Figure 2 illustrates a filament according to one embodiment of the invention. In this example, the filament has a circular section, but the invention is not limited to a particular geometry. When the filament is not circular, consider the diameter of a circular filament whose section has an identical area.
    The diameter of the filament is typically between 1 and 3 mm, the most prevalent diameters at present for the 3D printing filaments being 1.75 mm, 2.85 mm and 3 mm. However, these values are not limiting and may evolve according to the needs of the market.
    The manufacture of the filament comprises the formation of the core by extrusion through a suitable die. The envelope may be formed by extrusion at the same time as the core (coextrusion) or by another recovery technique implemented during the manufacture of the core or later, in recovery. The coextrusion process is preferred in that it provides the core and shell in a single operation.
    The manufacturing process is configured to ensure a very precise tolerance on the diameter of the filament, of the order of a hundredth of a millimeter. In this regard, it should be noted that brushcutter cutting lines, which typically have a diameter of the same order of magnitude as the 3D printing filaments described herein, are not suitable for 3D printing. Indeed, the drive mechanism of the filament in the printer requires a very high dimensional accuracy of the filament, the tolerance on the diameter of the filament being, as indicated above, of the order of a hundredth of a millimeter. Cutting lines for brush cutters do not require such dimensional accuracy and have a tolerance on the diameter of the order of a tenth of a millimeter. As a result, such yarns could not be properly driven into a 3D printer, the diameter variations resulting in uneven yarn drive and rapidly causing clogging of the print head. The envelope 11 forms a layer completely surrounding the core 10 and has a substantially constant thickness over the entire periphery of the core and over the length of the filament. The thickness of the envelope is preferably as thin as possible to fulfill a barrier function (examples of which are described below), without significantly affecting the properties of the object obtained by 3D printing. Thus, the material of the envelope forms a small proportion of the material of the object formed by 3D printing, which consists of an intimate mixture of the materials of the core and the envelope.
    For example, for a filament 1.75 mm in diameter, the thickness of the envelope is advantageously between 0.05 mm and 0.20 mm; for a filament of 2.85 or 3 mm in diameter, the thickness of the envelope may be between 0.05 mm and 0.30 mm.
    According to one embodiment, the core comprises a filler in the form of particles such as fibers or a powder.
    Among the preferred fillers, mention may be made of: glass, aramid, carbon, poly (p-phenylene-2,6-benzobisoxazole) (PBO) sold under the name Zylon ™, which is used in many products requiring high mechanical strength and good thermal stability, - a metal, - a ceramic.
    Said fillers may be in the form of powder or cut fibers. Optionally, it may also be continuous fibers. In the case of chopped or ground fibers, the diameter of the fibers is typically between 18 and 70 μm. The length of the fibers can range from 50 μm up to 100 μm, even up to 500 μm, long fibers having the effect of binding the object manufactured by 3D printing from such a filament.
    Moreover, depending on the nature and the quantity of charges incorporated in the material of the core, said charges may have for one or more of the following effects: - increase the density of the object, - limit the withdrawal of the object after printing - improve the mechanical, thermal and / or electrical conductivity properties of the object, - modify the appearance of the object.
    For example, a high proportion of metal charges in the core makes it possible to give the object a metallic appearance, to increase its density and to increase its thermal and / or electrical conductivity.
    According to another example, a filler such as glass fibers makes it possible to block the shrinkage of the object and to increase its mechanical strength.
    Naturally, the skilled person may use the aforementioned charges in combination, and may possibly add other charges.
    Unlike the soul, the envelope is devoid of charges.
    Thus, the envelope has no abrasiveness likely to damage the components of the 3D printer.
    Comparative tests were thus carried out with, on the one hand, a filament consisting solely of a thermoplastic material filled with glass fibers and, on the other hand, a filament according to the invention, comprising a core made of a thermoplastic material loaded with glass fibers and an envelope made of an unfilled thermoplastic material and miscible with the material of the core. With the first filament, the 3D printer clogged in a few minutes and disassembly of the printer showed a net wear of the filament drive rollers. With the second filament, the printer could be used for several hours without showing signs of wear.
    Moreover, the envelope may advantageously be made of a material forming a moisture barrier. Thus, even if the material of the core has a significant moisture uptake, the envelope prevents the penetration of water within the filament and thus limits the dimensional variations of the filament.
    For example, the core may comprise PA 6/66/12, which has a moisture recovery rate of 4.5% in an atmosphere at 20 ° C having a moisture content of 50%.
    In another example, the core may comprise PA6 / 66 or PA6, which also have a high rate of moisture recovery.
    These polyamides, whether loaded or not, have interesting mechanical properties, making it possible to obtain objects having a good mechanical strength, including temperature. The envelope is advantageously made of PA12, PAIO or PA1010, which have a moisture recovery rate lower than that of PA6, PA6 / 66 or PA6 / 66/12. Thus, the PA12 has a relatively low rate of moisture uptake (of the order of 0.8%) and has the advantage of adhering perfectly to the material of the core (in particular as regards PA6 / 66 / 12). PAIO has an even lower moisture recovery rate (around 0.4%). More generally, any impervious material and / or having a low rate of moisture uptake can be used to form the envelope, provided that it has a sufficient adhesion to the material of the core (which is not limited to polyamide). This prevents the formation of bubbles in the core during the heating of the filament. The envelope may also form a thermal barrier to prevent excessive softening of a filament whose core would include a thermally conductive filler, typically comprising one or more metals. Said envelope being devoid of such a load, it provides a thermal insulation of the core which avoids the clogging problem mentioned in the preamble.
    Naturally, depending on the chosen material, the envelope can fulfill all or part of the various functions mentioned above.
    Finally, it goes without saying that the examples that we have just given are only particular illustrations in no way limiting as to the fields of application of the invention.
    权利要求:
    Claims (16)
    [1" id="c-fr-0001]
    1. Filament (1) for 3D printing, characterized in that it has a core (10) having a first composition and an envelope (11) surrounding the core (10) having a second composition different from that of the soul (10), the core and the envelope each comprising a thermoplastic material, the thermoplastic material of the envelope being miscible with that of the core.
    [2" id="c-fr-0002]
    2. Filament according to claim 1, wherein the core (10) comprises a filler in the form of fibers or a powder and the casing (11) is free of a load.
    [3" id="c-fr-0003]
    3. Filament according to claim 2, wherein the load of the core (10) comprises fibers of glass, carbon, poly (p-phenylene-2,6-benzobisoxazole) (PBO) and / or aramid .
    [4" id="c-fr-0004]
    4. Filament according to claim 3, wherein the fibers are chopped or ground fibers having a diameter of between 18 and 70 pm and a length of between 50 and 500 microns.
    [5" id="c-fr-0005]
    The filament of claim 2, wherein the core charge (10) comprises a thermally conductive particle powder.
    [6" id="c-fr-0006]
    The filament of claim 5, wherein the thermally conductive particles comprise metal particles.
    [7" id="c-fr-0007]
    7. Filament according to one of claims 1 to 6, wherein the soul (10) comprises polyamide and the envelope (11) is made of a material impermeable to moisture and / or having a rate of moisture recovery less than the polyamide of the soul.
    [8" id="c-fr-0008]
    The filament of claim 7, wherein the core comprises PA6, PA6 / 66 or PA6 / 66/12.
    [9" id="c-fr-0009]
    9. Filament according to one of claims 7 or 8, wherein the material of the casing (11) comprises polyamide 12, polyamide 10 or polyamide 1010.
    [10" id="c-fr-0010]
    10. Filament according to one of claims 1 to 9, wherein the casing has a thickness between 0.05 and 0.30 mm, preferably between 0.05 and 0.20 mm.
    [11" id="c-fr-0011]
    11. Filament according to one of claims 1 to 10, wherein the diameter of the filament is between 1 and 3 mm.
    [12" id="c-fr-0012]
    12. A method of manufacturing a filament (1) for printing 3P according to one of claims 1 to 11, characterized in that the casing (11) is formed around the core (10) by coextrusion.
    [13" id="c-fr-0013]
    13. A method of manufacturing an object by 3D printing, wherein a filament (1) according to one of claims 1 to 11 is used.
    [14" id="c-fr-0014]
    14. Process for limiting the withdrawal of a manufactured object by 3D printing by means of a load contained in a filament, in which a filament (1) according to one of claims 2 to 6 is provided, said filament being drawn towards a print head in which said filament is locally heated, and the mulled filament is extruded through a nozzle of a 3D printer so as to form the object by superposition of successive layers, the envelope preserving the components of the printer 30 wear by the load of the core.
    [15" id="c-fr-0015]
    15. Process for controlling the softening of a filament comprising a charge of thermally conductive fibers during the manufacture of an object by 3D printing, in which a filament (1) according to one of Claims 5 or 6 is provided. threading said filament vem a print head in which said filament is locally heated, and extruding the molten filament through a nozzle of a printer 30 so as to form the object by superimposing successive layers, wrapping you (11) forming a thermally insulating barrier limiting the softening of the filament upstream of the area of the print head where it is heated.
    [16" id="c-fr-0016]
    16. A method for preventing the formation of bubbles during the manufacture of an object by 3D printing with a filament comprising polyamide, wherein a filament (1) is used according to one of claims 7 to 9, envelope (11) forming a barrier to moisture absorption by the filament.
    类似技术:
    公开号 | 公开日 | 专利标题
    FR3052386A1|2017-12-15|FILAMENT FOR 3D PRINTING, METHOD FOR MANUFACTURING SUCH FILAMENT, AND METHOD FOR MANUFACTURING OBJECT BY 3D PRINTING
    EP0541441A1|1993-05-12|Process of manufacturing a composite moulded product
    EP0281447A1|1988-09-07|Process for producing thermoplastic polymer profiles by pultrusion, apparatus and products obtained
    CA2347147A1|2000-05-04|Hollow solid generated by rotation and method for making same
    CA2421098C|2012-09-04|Ultrasound bonding process
    WO2005084902A1|2005-09-15|Synthetic multilayer object
    FR2949791A1|2011-03-11|PROCESS FOR PRODUCING PRE-IMPREGNATED FIBROUS MATERIAL OF THERMOPLASTIC POLYMER
    WO2017017388A1|2017-02-02|Method for preparing a fiber material, pre-impregnated by a thermoplastic polymer, using a liquid crystal polymer
    FR2672252A1|1992-08-07|ONE-PIECE SYNTHETIC RESIN WHEEL.
    EP2367891B1|2016-09-14|Composition of hot-melt, self-adhesive particles and sticking method using same
    EP1348532A1|2003-10-01|Ultrasonic bonding method
    WO1997021861A2|1997-06-19|Method for making a glass mat and resulting product
    FR2948895A1|2011-02-11|MANUFACTURE AND USE OF A PROFILE REINFORCED IN THERMOPLASTIC MATERIAL
    EP3230513B1|2019-05-01|Textile reinforcement for pultrusion and method for the production thereof
    FR2852551A1|2004-09-24|Acoustic and/or vibration insulation material is made from a mixture of elastic particles and a plastomer resin, rolled into strips
    EP2117805A2|2009-11-18|Cooling jig for extruding pctfe strings and method for extruding pctfe strings
    EP2900451B1|2018-10-31|Process for producing a thermoplastic composite material reinforced with carbon nanotubes
    FR2739803A1|1997-04-18|Production of thermoplastic cored e.g. polypropylene honeycomb, sandwich panel
    EP0077733B1|1986-06-18|Process for preparing composite materials of carbon fibres and a thermoplastic material, the composite materials and their applications
    EP3768482A2|2021-01-27|Web of impregnated fibrous material, production method thereof and use of same for the production of three-dimensional composite parts
    FR3100476A1|2021-03-12|MANUFACTURING PROCESS OF A COMPOSITE PART REINFORCED BY NANOTUBES
    FR3100007A1|2021-02-26|Stone filament for a 3D printer, method of manufacturing such a filament and method of manufacturing an object from such a filament
    EP2933092A1|2015-10-21|Process and mounting of a film upon extrusion of a tube for packaging
    EP3332950B1|2020-10-21|Vacuum cover for a method for infusion of composite materials comprising a fluoroelastomer, use and manufacturing method
    EP1144745B1|2007-12-26|Method for making a mat and resulting products
    同族专利:
    公开号 | 公开日
    WO2017212190A1|2017-12-14|
    FR3052386B1|2020-01-10|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US20120231225A1|2010-09-17|2012-09-13|Stratasys, Inc.|Core-shell consumable materials for use in extrusion-based additive manufacturing systems|
    WO2015077262A1|2013-11-19|2015-05-28|Guill Tool & Engineering|Coextruded, multilayered and multicomponent 3d printing inputs|
    WO2016159259A1|2015-03-31|2016-10-06|キョーラク株式会社|Filament resin molding, three-dimensional object fabrication method, and filament resin molding manufacturing method|
    WO2017009190A1|2015-07-14|2017-01-19|Basf Se|Filaments based on a coated core material|CN111270346A|2018-12-05|2020-06-12|沙特基础工业全球技术有限公司|Core-shell filaments and methods of forming the same and articles formed therefrom|US9889607B2|2014-02-19|2018-02-13|Makerbot Industries, Llc|Three-dimensional printer with integrated coloring system|EP3375608B1|2017-03-17|2021-05-05|Ricoh Company, Ltd.|Resin powder for solid freeform fabrication and device for solid freeform fabrication object|
    DE102018102731A1|2018-02-07|2019-08-08|Aim3D Gmbh|Method and device for the additive production of a workpiece or component of reinforced plastics|
    EP3737549A4|2018-02-08|2021-10-06|Essentium, Inc.|Multiple layer filament and method of manufacturing|
    KR20200130330A|2018-03-06|2020-11-18|바스프 에스이|Filament based on core material comprising fibrous filler|
    WO2021028795A1|2019-08-15|2021-02-18|3M Innovative Properties Company|Core-sheath filament with a thermally conductive pressure-sensitive adhesive core|
    RU2738388C1|2020-04-01|2020-12-11|Автономная некоммерческая образовательная организация высшего образования "Сколковский институт науки и технологий"|Coaxial filament for 3d printer|
    法律状态:
    2017-06-15| PLFP| Fee payment|Year of fee payment: 2 |
    2017-12-15| PLSC| Search report ready|Effective date: 20171215 |
    2018-06-13| PLFP| Fee payment|Year of fee payment: 3 |
    2019-06-12| PLFP| Fee payment|Year of fee payment: 4 |
    2020-06-27| PLFP| Fee payment|Year of fee payment: 5 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1655289A|FR3052386B1|2016-06-09|2016-06-09|FILAMENT FOR 3D PRINTING, METHOD FOR MANUFACTURING SUCH A FILAMENT, AND METHOD FOR MANUFACTURING AN OBJECT BY 3D PRINTING|
    FR1655289|2016-06-09|FR1655289A| FR3052386B1|2016-06-09|2016-06-09|FILAMENT FOR 3D PRINTING, METHOD FOR MANUFACTURING SUCH A FILAMENT, AND METHOD FOR MANUFACTURING AN OBJECT BY 3D PRINTING|
    PCT/FR2017/051468| WO2017212190A1|2016-06-09|2017-06-09|Filament for 3d printing, method for producing such a filament, and method for producing an object using 3d printing|
    [返回顶部]