WO2013034841A1 - Use of a method of manufacturing a part layer by layer - Google Patents

Use of a method of manufacturing a part layer by layer Download PDF

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Publication number
WO2013034841A1
WO2013034841A1 PCT/FR2012/051972 FR2012051972W WO2013034841A1 WO 2013034841 A1 WO2013034841 A1 WO 2013034841A1 FR 2012051972 W FR2012051972 W FR 2012051972W WO 2013034841 A1 WO2013034841 A1 WO 2013034841A1
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pigment
layer
phosphorescent
powder
mixture
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PCT/FR2012/051972
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French (fr)
Inventor
Gilles Lemoine
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DP3i - DEVELOPPEMENT PRODUCTION INDUSTRIALISATION D'IDEES INNOVANTES
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Publication of WO2013034841A1 publication Critical patent/WO2013034841A1/en

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    • 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

Definitions

  • the present invention relates to a use of a method of manufacturing a piece layer by layer. It also relates to a method of manufacturing a phosphorescent part, as well as the part obtained by this method.
  • a photoluminescent material is a material which by its exposure to light passes from a so-called fundamental stable state to an excited state. This excited state is maintained as long as the material is exposed to light. When this light diminishes or disappears, the matter passes more or less quickly from the excited state where it was in the ground state. During this passage between the excited state and the ground state, light radiation is emitted. It is this radiation that gives matter its capacity to be seen in the dark. Photoluminescence can be caused by ultraviolet, visible or infrared radiation.
  • Such a photoluminescent material is usually used to coat surfaces or to make objects that one wishes to be able to continue to see when the brightness decreases or disappears completely.
  • Fluorescence results from an intramolecular process that does not depend on ambient conditions. It is a luminescence usually stopping when the excitation stops. Phosphorescence is linked to the crystalline structure and depends on the temperature. Phosphorescence is a luminescence that persists for some time after the excitation is stopped, and the persistence time can range from a fraction of a second to several days.
  • Obtaining a phosphorescent part is usually achieved by applying a phosphorescent paint on the part. It is then necessary to apply a first reflective layer, then at least one other layer containing phosphorescent pigments.
  • a first reflective layer for example in the case of an extremely complex piece, that is to say non-demoldable, it is impossible to cover the part on the entire surface thereof, resulting in an inhomogeneity in the phosphorescent rendering, because not to be able to cover all surfaces.
  • the visual effect of phosphorescence decreases if the part is scratched since the surface coating is removed.
  • Another possible means of manufacture is the injection of phosphorescent pigment-filled plastics material (or a pigment-filled resin casting) into molds, which, on the one hand, does not make it possible to obtain objects without any constraint on their shape. and, on the other hand, gives rise to inhomogeneity in the distribution of the pigments in the volume of the part because of the differences in density between the polymers and the pigments used.
  • the present invention aims to remedy these disadvantages.
  • the subject of the invention is thus the use of a method for manufacturing a piece layer by layer, starting from layers of a mixture comprising a polymer powder and a powder of a phosphorescent pigment, the weight of the pigment not exceeding 90% of the total weight of the mixture, to impart phosphorescence, and in particular homogeneous phosphorescence, to said part.
  • homogeneous phosphorescence in the sense of the invention is meant a light emission, without shading effect, throughout the room and at any point in the room, that is to say in the inner parts (not visible surfaces) as external (visible surfaces).
  • the layer-by-layer manufacturing method may for example be a rapid prototyping method such as stereolithography, which uses a UV laser to photopolymerize a liquid resin layer by layer, or a selective laser sintering process which uses, for example an infra-red laser to construct the object from a solid polymer.
  • a rapid prototyping method such as stereolithography, which uses a UV laser to photopolymerize a liquid resin layer by layer
  • a selective laser sintering process which uses, for example an infra-red laser to construct the object from a solid polymer.
  • SLS Selective laser sintering
  • SLS Selective Laser Sintering
  • This method uses a laser to transform a powdery material, comprising a mixture of metal powders and polymer powder, into a solid object by selective sintering without external pressure.
  • Selective laser sintering is preferably computer assisted.
  • the mixture of powders is heated to a temperature of a few degrees Celsius lower than the melting temperature of the polymer, for example to a temperature of 1 to 10 ° C. lower than the melting point. of the polymer.
  • the energy required for fusion is then provided by the laser.
  • the polymer may for example be chosen from thermoplastic organic polymers such as polyamides (for example nylon 6, nylon 11, nylon 12), amide copolymers (for example nylon 6-12), polyacetates, polyesters and the like.
  • PEEK PolyEtherEtherKetone in English.
  • Preferred polymers are polyamides and polyetheretherketone.
  • the phosphorescent pigment may be chosen from aluminate bases, or silicates or aluminosilicates doped with europium (Eu 2+ ) and optionally co-doped with a lanthanide (Ln 3+ ).
  • the pigment is based on strontium aluminate
  • the strontium aluminate can be doped with europium (SrAl 2 O 4 : Eu 2+ ) and can be optionally co-doped with a lanthanide such as dysprosium (SrAl 2 O 4 : Eu 2+ , Dy 3+ ).
  • the zinc sulfide can be doped with copper (ZnS: Cu) and can be optionally co-doped with cobalt (ZnS: Cu, Co).
  • the mixture can comprise from 10 to 91% by weight of polymer, and preferably from 25 to 85% by weight.
  • the mixture may comprise from 9 to 90% by weight of phosphorescent pigment, and preferably from 15 to 75% by weight, and especially from 30 to 75% by weight, and especially from 40 to 75% by weight, from 50 to 75% by weight. % by weight or 60 to 75% by weight.
  • the average particle size of the pigment may be from 5 to 120 ⁇ m, and preferably from 10 to 80 ⁇ m.
  • the average particle size of the polymer may be between 1 and 120 ⁇ m.
  • the powder mixture can consist of a polymer powder and a phosphorescent pigment powder (s).
  • the mixture may also include adjuvants. It is possible, for example, to perform a surface functionalization treatment of the pigments with aminosilane in order to improve the adhesion between the polymer matrix and the pigments. It is also possible to add ceramic pigments such as metal oxides to modify the color of the pieces, such as for example Ti0 2 or Al 2 0 3 to whiten the piece.
  • the invention also relates to a method of manufacturing a phosphorescent part.
  • the process according to the invention comprises a layer-by-layer manufacturing step, from a mixture comprising a polymer powder and a powder of a phosphor-based pigment based on SrAl 2 O 4 and / or ZnS, the weight the pigment does not exceed 90% of the total weight of the mixture, the average particle size of the pigment being between 5 and 120 pm.
  • the process may be selective laser sintering.
  • the average particle size of the pigment is between 5 and 120 ⁇ m, and preferably between 10 and 80 ⁇ m.
  • the components and proportions of the powder mixture may be selected from those described above.
  • the invention also relates to the part obtained by this method.
  • the phosphorescent parts obtained by the layer-by-layer manufacturing process can for example be used as security objects (emergency exit), decorative objects, artistic creations, dresses, hats, gloves, shoes, costume jewelery, bracelets, eyewear, rings. .
  • FIG. 1 schematically illustrates a device making it possible to implement the process according to the invention.
  • Example 1 Manufacture of a phosphorescent part with SrAl 2 0 4 as a pigment
  • a mixture of powders comprising at least two different types of powder (polymer and phosphorescent pigment) was prepared. Each grade of powder is accurately weighed so as to obtain a volume fraction of pigment in the final piece of 50%.
  • the powders are preferably mixed homogeneously using a turbulat, which will make it possible to obtain parts having mechanical properties and homogeneous phosphorescence. About ten minutes are required to mix 10 kg of powders.
  • phosphorescent pieces were prepared by selectively laser sintering the powder mixture consisting of 15% by weight of a phosphorescent powder of SrAl 2 O 4 having a particle size of between 10 and 60 ⁇ m and 85% by weight of a polyamide powder which is a nylon 12 powder having an average particle size of 60 ⁇ m.
  • Selective laser sintering can be implemented using a device 1 as illustrated in FIG.
  • the selective laser sintering device 1 comprises a powder supply tank 2 in which the mixture is placed, a powder supply and distribution roller 3, and a laser 4.
  • the laser 4 is for example a C0 2 laser with a power of 35 W.
  • the laser beam is directed via a mirror 5 towards the powder zone that it is desired to sinter, under a preferably neutral atmosphere, for example under a nitrogen atmosphere. .
  • the process uses a manufacturing platform heated to a temperature close to the melting point of the polymer.
  • the laser traces the layer-by-layer form and locally supplies, to each successive layer of the initial powder mixture, sufficient thermal energy to bring the polymer to a temperature causing it to melt.
  • Unsintered powders naturally provide support for the following layers.
  • the mobile work platform descends from the thickness of a layer, the displacement of the vertical part being provided by a piston 6.
  • a new layer of powder is then spread by the roller 3 and the cycle starts again to build the part layer by layer from bottom to top.
  • another mechanical system could be used, such as a scraper. Properties of the obtained parts
  • the parts obtained after sintering have a homogeneous shrinkage of 2 ⁇ 0.2% along the horizontal axes x and y, and 1.3 ⁇ 0.2% along the vertical axis z.
  • the average Shore D hardness is 70 ⁇ 2. It is 64 ⁇ 2 for the same piece without pigment or that of Example 5.
  • the phosphorescence is homogeneous.
  • Example 1 The procedure of Example 1 was repeated, but using a powder mixture consisting of 28% by weight of SrAl 2 O 4 pigment and 72% by weight of a polyamide powder which was a nylon 12 powder. .
  • the parts obtained after sintering have a homogeneous shrinkage of
  • Example 2 2 ⁇ 0.2% along the x and y axes and 1.3 ⁇ 0.2% along the z axis.
  • the average Shore D hardness is improved compared to Example 1, it is 74 ⁇ 2.
  • the phosphorescence is homogeneous.
  • Example 3 Manufacture of a phosphorescent part with ZnS as pigment
  • Example 1 The procedure of Example 1 was repeated, but using a mixture of powders consisting of 25% by weight of pigment (ZnS: Cu) and 75% by weight of a polyamide powder which is a nylon powder. 12.
  • the pieces obtained after sintering have a homogeneous shrinkage of 2 ⁇ 0.2% along the x and y axes and 1.3 ⁇ 0.2% along the z axis.
  • the average Shore D hardness is improved compared to the piece without pigment, it is 70 ⁇ 2.
  • the phosphorescence is homogeneous.
  • Example 4 Increase in ZnS rate
  • Example 1 The procedure of Example 1 was repeated, but using a mixture of powders consisting of 45% by weight of pigment (ZnS: Cu) and 55% by weight of a polyamide powder which is a nylon 12 powder. .
  • the pieces obtained after sintering have a homogeneous shrinkage of 2 ⁇ 0.2% along the x and y axes and 1.3 ⁇ 0.2% along the z axis.
  • the average Shore D hardness is improved compared to Example 3, it is 74 ⁇ 2.
  • the phosphorescence is homogeneous.
  • EXAMPLE 5 Very Complex Piece Part Coated with Phosphorescent Paint The procedure of Example 1 was repeated, but using a powder consisting solely of polyamide nylon 12. The part obtained is then covered with a phosphorescent paint with basis of SrAI 2 0 4 .
  • the pieces obtained after sintering have a homogeneous shrinkage of 2 ⁇ 0.2% along the x and y axes and 1.3 ⁇ 0.2% along the z axis.
  • the average Shore D hardness is 64 ⁇ 2. Phosphorescence is not homogeneous.

Abstract

The aim of the invention is the use of a method of manufacturing a part layer by layer, using layers of a mixture comprising a polymer powder and a phosphorescent pigment powder, the weight of the pigment not exceeding 90% of the total weight of the mixture, to give said part a phosphorescent quality. Figure to be published: Figure

Description

UTILISATION D'UN PROCEDE DE FABRICATION D'UNE PIECE COUCHE  USE OF A METHOD FOR MANUFACTURING A LAYERED PIECE
PAR COUCHE  BY LAYER
La présente invention a pour objet une utilisation d'un procédé de fabrication d'une pièce couche par couche. Elle a également pour objet un procédé de fabrication d'une pièce phosphorescente, ainsi que la pièce obtenue par ce procédé. The present invention relates to a use of a method of manufacturing a piece layer by layer. It also relates to a method of manufacturing a phosphorescent part, as well as the part obtained by this method.
Une matière photoluminescente est une matière qui par son exposition à la lumière passe d'un état stable dit fondamental à un état excité. Cet état excité est maintenu tant que la matière est exposée à la lumière. Lorsque cette lumière s'amenuise ou disparaît, la matière passe plus ou moins rapidement de l'état excité où elle se trouvait à l'état fondamental. Lors de ce passage entre l'état excité et l'état fondamental, un rayonnement lumineux est émis. C'est ce rayonnement qui donne à la matière sa capacité à être vue dans l'obscurité. La photoluminescence peut être provoquée par un rayonnement ultraviolet, visible ou infrarouge.  A photoluminescent material is a material which by its exposure to light passes from a so-called fundamental stable state to an excited state. This excited state is maintained as long as the material is exposed to light. When this light diminishes or disappears, the matter passes more or less quickly from the excited state where it was in the ground state. During this passage between the excited state and the ground state, light radiation is emitted. It is this radiation that gives matter its capacity to be seen in the dark. Photoluminescence can be caused by ultraviolet, visible or infrared radiation.
Une telle matière photoluminescente est habituellement utilisée pour revêtir des surfaces ou fabriquer des objets que l'on souhaite pouvoir continuer à voir lorsque la luminosité diminue ou disparaît complètement.  Such a photoluminescent material is usually used to coat surfaces or to make objects that one wishes to be able to continue to see when the brightness decreases or disappears completely.
On distingue deux types de photoluminescence : la fluorescence et la phosphorescence. La fluorescence résulte d'un processus intramoléculaire ne dépendant pas des conditions ambiantes. Il s'agit d'une luminescence s'arrêtant généralement lorsque cesse l'excitation. La phosphorescence est quant à elle liée à la structure cristalline et dépend de la température. La phosphorescence est une luminescence persistant un certain temps après l'arrêt de l'excitation, le temps de persistance pouvant aller d'une fraction de seconde à plusieurs jours.  There are two types of photoluminescence: fluorescence and phosphorescence. Fluorescence results from an intramolecular process that does not depend on ambient conditions. It is a luminescence usually stopping when the excitation stops. Phosphorescence is linked to the crystalline structure and depends on the temperature. Phosphorescence is a luminescence that persists for some time after the excitation is stopped, and the persistence time can range from a fraction of a second to several days.
La suite de la description est consacrée à la phosphorescence.  The rest of the description is devoted to phosphorescence.
L'obtention d'une pièce phosphorescente est habituellement réalisée par l'application d'une peinture phosphorescente sur la pièce. Il faut alors appliquer une première couche réfléchissante, puis au moins une autre couche contenant des pigments phosphorescents. Lorsque la pièce est de forme complexe, par exemple dans le cas d'une pièce extrêmement complexe, c'est- à-dire non démoulable, il est impossible de recouvrir la pièce sur la totalité de sa surface, ce qui entraîne une inhomogénéité dans le rendu phosphorescent, du fait de ne pas pouvoir recouvrir toutes les surfaces. En outre, l'effet visuel de phosphorescence diminue si l'on raye la pièce puisque le revêtement de surface s'enlève. Obtaining a phosphorescent part is usually achieved by applying a phosphorescent paint on the part. It is then necessary to apply a first reflective layer, then at least one other layer containing phosphorescent pigments. When the piece is of shape complex, for example in the case of an extremely complex piece, that is to say non-demoldable, it is impossible to cover the part on the entire surface thereof, resulting in an inhomogeneity in the phosphorescent rendering, because not to be able to cover all surfaces. In addition, the visual effect of phosphorescence decreases if the part is scratched since the surface coating is removed.
Un autre moyen de fabrication possible est l'injection de matière plastique chargée de pigments phosphorescents (ou une coulée de résine chargée de pigments) dans des moules, ce qui d'une part, ne permet pas d'obtenir des objets sans contrainte de forme, et d'autre part engendre une inhomogénéité dans la répartition des pigments dans le volume de la pièce du fait des différences de densité entre les polymères et les pigments utilisés.  Another possible means of manufacture is the injection of phosphorescent pigment-filled plastics material (or a pigment-filled resin casting) into molds, which, on the one hand, does not make it possible to obtain objects without any constraint on their shape. and, on the other hand, gives rise to inhomogeneity in the distribution of the pigments in the volume of the part because of the differences in density between the polymers and the pigments used.
Le document US 2004/0232583 mentionne des pigments phosphorescents, qui sont toutefois utilisés pour modifier la couleur des objets fabriqués. Il n'est pas fait mention de leur utilisation, en liaison avec le procédé mis en œuvre, pour conférer de la phosphorescence auxdits objets. La coloration et la phosphorescence sont en effet deux phénomènes bien distincts. La coloration provient des ondes lumineuses réfléchies par un objet, tandis que la phosphorescence est une propriété qui permet de continuer à voir l'objet lorsque les ondes lumineuses disparaissent.  Document US 2004/0232583 mentions phosphorescent pigments, which are however used to modify the color of the objects manufactured. There is no mention of their use, in connection with the method used, to impart phosphorescence to said objects. Staining and phosphorescence are two distinct phenomena. The coloring comes from the light waves reflected by an object, while the phosphorescence is a property that allows to continue to see the object when the light waves disappear.
La présente invention vise à remédier à ces inconvénients.  The present invention aims to remedy these disadvantages.
Elle propose un procédé permettant la fabrication de pièces de formes simples ou complexes, et qui présentent une phosphorescence particulièrement homogène.  It proposes a process for the manufacture of parts of simple or complex shapes, which have a particularly homogeneous phosphorescence.
La demanderesse a découvert de manière surprenante que ces propriétés remarquables de phosphorescence pouvaient être obtenues en mettant en œuvre un procédé inédit pour l'homme du métier des pièces phosphorescentes, à savoir un procédé de fabrication des pièces couche par couche, et notamment un procédé de frittage sélectif par laser. Elle a été également particulièrement surprise de constater que les propriétés de phosphorescence des pièces obtenues par ce procédé persistaient même lorsque la pièce est rayée ou entaillée, du fait de la grande homogénéité de phosphorescence conférée à la pièce par le procédé. L'invention a ainsi pour objet l'utilisation d'un procédé de fabrication d'une pièce couche par couche, à partir de couches d'un mélange comprenant une poudre de polymère et une poudre d'un pigment phosphorescent, le poids du pigment n'excédant pas 90% du poids total du mélange, pour conférer de la phosphorescence, et notamment une phosphorescence homogène, à ladite pièce. The Applicant has surprisingly discovered that these remarkable properties of phosphorescence could be obtained by implementing a novel method for those skilled in the art of phosphorescent parts, namely a method of manufacturing the parts layer by layer, and in particular a method of selective sintering by laser. It was also particularly surprising to note that the phosphorescence properties of the pieces obtained by this method persisted even when the piece is scratched or notched, because of the high homogeneity of phosphorescence imparted to the piece by the process. The subject of the invention is thus the use of a method for manufacturing a piece layer by layer, starting from layers of a mixture comprising a polymer powder and a powder of a phosphorescent pigment, the weight of the pigment not exceeding 90% of the total weight of the mixture, to impart phosphorescence, and in particular homogeneous phosphorescence, to said part.
Par « phosphorescence homogène » au sens de l'invention, on entend une émission lumineuse, sans effet d'ombrage, dans l'ensemble de la pièce et à n'importe quel endroit de la pièce, c'est-à-dire dans les parties intérieures (surfaces non visibles) comme extérieures (surfaces visibles).  By "homogeneous phosphorescence" in the sense of the invention is meant a light emission, without shading effect, throughout the room and at any point in the room, that is to say in the inner parts (not visible surfaces) as external (visible surfaces).
Le procédé de fabrication couche par couche peut par exemple être un procédé de prototypage rapide tel que la stéréolithographie, qui utilise un laser UV pour photo-polymériser couche après couche une résine liquide, ou encore un procédé de frittage sélectif par laser qui utilise par exemple un laser infra- rouge pour construire l'objet à partir d'un polymère solide.  The layer-by-layer manufacturing method may for example be a rapid prototyping method such as stereolithography, which uses a UV laser to photopolymerize a liquid resin layer by layer, or a selective laser sintering process which uses, for example an infra-red laser to construct the object from a solid polymer.
Le frittage sélectif par laser, également appelé Sélective Laser Sintering (SLS) en langue anglaise, est un procédé permettant la mise en forme d'une pièce par apports successifs de matière sous forme de poudres.  Selective laser sintering (SLS), also known as Selective Laser Sintering (SLS), is a process that allows a part to be shaped by successive additions of material in the form of powders.
Ce procédé utilise un laser pour transformer un matériau sous forme de poudres, comprenant un mélange de poudres métalliques et de poudre de polymère, en un objet solide par frittage sélectif sans pression extérieure.  This method uses a laser to transform a powdery material, comprising a mixture of metal powders and polymer powder, into a solid object by selective sintering without external pressure.
Le frittage sélectif par laser est de préférence assisté par ordinateur. Selective laser sintering is preferably computer assisted.
Dans un mode de réalisation particulier, le mélange de poudres est chauffé jusqu'à une température inférieure de quelques degrés Celsius à la température de fusion du polymère, par exemple jusqu'à une température inférieure de 1 à 10 °C à la température de fusion du polymère. L'énergie nécessaire à la fusion est ensuite apportée par le laser. In a particular embodiment, the mixture of powders is heated to a temperature of a few degrees Celsius lower than the melting temperature of the polymer, for example to a temperature of 1 to 10 ° C. lower than the melting point. of the polymer. The energy required for fusion is then provided by the laser.
Le polymère peut être par exemple choisi parmi les polymères organiques thermoplastiques tels que les polyamides (par exemple de type Nylon 6, Nylon 11, Nylon 12), les copolymères d'amide (par exemple le nylon 6-12), les polyacétates, les polyéthylènes, ainsi que le polyétheréthercétone, désigné par le sigle PEEK (PolyEtherEtherKetone en langue anglaise). Les polymères préférés sont les polyamides et le polyétheréthercétone.The polymer may for example be chosen from thermoplastic organic polymers such as polyamides (for example nylon 6, nylon 11, nylon 12), amide copolymers (for example nylon 6-12), polyacetates, polyesters and the like. polyethylenes, as well as polyetheretherketone, designated by the acronym PEEK (PolyEtherEtherKetone in English). Preferred polymers are polyamides and polyetheretherketone.
Le pigment phosphorescent peut être choisi parmi les bases aluminates, ou silicates ou aluminosilicates dopées à l'europium (Eu2+) et éventuellement co-dopées par un lanthanide (Ln3+). The phosphorescent pigment may be chosen from aluminate bases, or silicates or aluminosilicates doped with europium (Eu 2+ ) and optionally co-doped with a lanthanide (Ln 3+ ).
De préférence, le pigment est à base d'aluminate de strontium Preferably, the pigment is based on strontium aluminate
(SrAI204) ou à base de sulfure de zinc (ZnS), ou un mélange de ces pigments. L'aluminate de strontium peut être dopé avec de l'europium (SrAI204 : Eu2+) et peut être éventuellement co-dopé avec un lanthanide tel que le dysprosium (SrAI204: Eu2+,Dy3+). Le sulfure de zinc peut être dopé avec du cuivre (ZnS :Cu) et peut être éventuellement co-dopé avec du cobalt (ZnS :Cu,Co). (SrAl 2 O 4 ) or based on zinc sulfide (ZnS), or a mixture of these pigments. The strontium aluminate can be doped with europium (SrAl 2 O 4 : Eu 2+ ) and can be optionally co-doped with a lanthanide such as dysprosium (SrAl 2 O 4 : Eu 2+ , Dy 3+ ). The zinc sulfide can be doped with copper (ZnS: Cu) and can be optionally co-doped with cobalt (ZnS: Cu, Co).
Le mélange peut comprendre de 10 à 91 % en poids de polymère, et de préférence de 25 à 85 % en poids.  The mixture can comprise from 10 to 91% by weight of polymer, and preferably from 25 to 85% by weight.
Le mélange peut comprendre de 9 à 90 % en poids de pigment phosphorescent, et de préférence de 15 à 75 % en poids, et notamment de 30 à 75% en poids, et notamment de 40 à 75% en poids, de 50 à 75% en poids ou encore de 60 à 75% en poids.  The mixture may comprise from 9 to 90% by weight of phosphorescent pigment, and preferably from 15 to 75% by weight, and especially from 30 to 75% by weight, and especially from 40 to 75% by weight, from 50 to 75% by weight. % by weight or 60 to 75% by weight.
La granulométrie moyenne du pigment peut être comprise entre 5 et 120 prri, et de préférence entre 10 et 80 pm.  The average particle size of the pigment may be from 5 to 120 μm, and preferably from 10 to 80 μm.
La granulométrie moyenne du polymère peut être comprise entre 1 et 120 pm.  The average particle size of the polymer may be between 1 and 120 μm.
Le mélange de poudres peut être constitué d'une poudre de polymère et d'une poudre de pigment(s) phosphorescent(s).  The powder mixture can consist of a polymer powder and a phosphorescent pigment powder (s).
Le mélange peut aussi comprendre des adjuvants. On peut par exemple réaliser un traitement de fonctionnalisation de surface des pigments avec de l'aminosilane afin d'améliorer l'adhérence entre la matrice de polymère et les pigments. On peut aussi ajouter des pigments céramiques tels que les oxydes métalliques pour modifier la couleur des pièces, comme par exemple Ti02 ou Al203 pour blanchir la pièce. The mixture may also include adjuvants. It is possible, for example, to perform a surface functionalization treatment of the pigments with aminosilane in order to improve the adhesion between the polymer matrix and the pigments. It is also possible to add ceramic pigments such as metal oxides to modify the color of the pieces, such as for example Ti0 2 or Al 2 0 3 to whiten the piece.
L'invention a également pour objet un procédé de fabrication d'une pièce phosphorescente.  The invention also relates to a method of manufacturing a phosphorescent part.
Le procédé selon l'invention comprend une étape de fabrication couche par couche, à partir d'un mélange comprenant une poudre de polymère et une poudre d'un pigment phosphorescent à base de SrAI204 et/ou de ZnS, le poids du pigment n'excédant pas 90% du poids total du mélange, la granulométrie moyenne du pigment étant comprise entre 5 et 120 pm. The process according to the invention comprises a layer-by-layer manufacturing step, from a mixture comprising a polymer powder and a powder of a phosphor-based pigment based on SrAl 2 O 4 and / or ZnS, the weight the pigment does not exceed 90% of the total weight of the mixture, the average particle size of the pigment being between 5 and 120 pm.
La demanderesse a constaté de manière surprenante qu'en utilisant ce pigment spécifique de granulométrie spécifique, on obtenait une pièce rigide présentant une tenue mécanique améliorée par rapport à la pièce qui est obtenue sans le pigment ou recouverte par le pigment en surface (peinture).  The applicant has found, surprisingly, that using this specific pigment of specific particle size, a rigid piece having improved mechanical strength with respect to the part obtained without the pigment or covered by the surface pigment (paint) is obtained.
Le procédé peut être le frittage sélectif par laser.  The process may be selective laser sintering.
La granulométrie moyenne du pigment est comprise entre 5 et 120 prri, et de préférence entre 10 et 80 pm.  The average particle size of the pigment is between 5 and 120 μm, and preferably between 10 and 80 μm.
Les composants et les proportions du mélange de poudre peuvent être choisis parmi ceux décrits plus haut.  The components and proportions of the powder mixture may be selected from those described above.
L'invention a également pour objet la pièce obtenue par ce procédé. Les pièces phosphorescentes obtenues par le procédé de fabrication couche par couche peuvent par exemple être utilisées comme objets de sécurité (sortie de secours), objets de décoration, créations artistiques, robes, chapeaux, gants, chaussures, bijoux fantaisie, bracelets, lunetterie, bagues.  The invention also relates to the part obtained by this method. The phosphorescent parts obtained by the layer-by-layer manufacturing process can for example be used as security objects (emergency exit), decorative objects, artistic creations, dresses, hats, gloves, shoes, costume jewelery, bracelets, eyewear, rings. .
D'autres caractéristiques et avantages de la présente invention apparaîtront plus clairement à la lecture des exemples suivants, auxquels elle n'est cependant pas limitée, la description étant faite en référence à la figure 1 qui illustre schématiquement un dispositif permettant de mettre en œuvre le procédé selon l'invention.  Other features and advantages of the present invention will appear more clearly on reading the following examples, to which it is however not limited, the description being made with reference to FIG. 1 which schematically illustrates a device making it possible to implement the process according to the invention.
Exemple 1 : fabrication d'une pièce phosphorescente avec SrAI204 comme pigment Example 1: Manufacture of a phosphorescent part with SrAl 2 0 4 as a pigment
Préparation de la poudre Preparation of the powder
On a préparé un mélange de poudres comprenant au moins deux natures de poudre différentes (polymère et pigment phosphorescent). Chaque nuance de poudre est pesée avec précision de sorte à obtenir une fraction volumique de pigment dans la pièce finale de 50 %. Les poudres sont de préférence mélangées de façon homogène à l'aide d'un turbulat, ce qui permettra d'obtenir des pièces présentant des propriétés mécaniques et de phosphorescence homogènes. Environ dix minutes sont nécessaires pour mélanger 10 kg de poudres. A mixture of powders comprising at least two different types of powder (polymer and phosphorescent pigment) was prepared. Each grade of powder is accurately weighed so as to obtain a volume fraction of pigment in the final piece of 50%. The powders are preferably mixed homogeneously using a turbulat, which will make it possible to obtain parts having mechanical properties and homogeneous phosphorescence. About ten minutes are required to mix 10 kg of powders.
Fabrication des pièces Parts manufacturing
On a préparé plusieurs pièces phosphorescentes en soumettant à un frittage sélectif par laser le mélange de poudres constitué de 15 % en poids d'une poudre phosphorescente de SrAI204 ayant une granulométrie comprise entre 10 et 60 pm et de 85 % en poids d'une poudre de polyamide qui est une poudre de Nylon 12 ayant une granulométrie moyenne de 60 pm. Several phosphorescent pieces were prepared by selectively laser sintering the powder mixture consisting of 15% by weight of a phosphorescent powder of SrAl 2 O 4 having a particle size of between 10 and 60 μm and 85% by weight of a polyamide powder which is a nylon 12 powder having an average particle size of 60 μm.
Le frittage sélectif par laser peut être mis en œuvre à l'aide d'un dispositif 1 tel qu'illustré à la figure 1.  Selective laser sintering can be implemented using a device 1 as illustrated in FIG.
Le dispositif 1 de frittage sélectif par laser comprend un réservoir 2 d'alimentation de poudre dans lequel est placé le mélange, un rouleau 3 d'apport et de répartition de poudre, ainsi qu'un laser 4.  The selective laser sintering device 1 comprises a powder supply tank 2 in which the mixture is placed, a powder supply and distribution roller 3, and a laser 4.
Le laser 4 est par exemple un laser C02 de puissance 35 W. Le faisceau laser est dirigé via un miroir 5 vers la zone de poudre que l'on souhaite fritter, sous une atmosphère de préférence neutre, par exemple sous atmosphère d'azote. The laser 4 is for example a C0 2 laser with a power of 35 W. The laser beam is directed via a mirror 5 towards the powder zone that it is desired to sinter, under a preferably neutral atmosphere, for example under a nitrogen atmosphere. .
Le procédé utilise une plate-forme de fabrication chauffée à une température proche de la température de fusion du polymère. Le laser trace la forme couche par couche et fournit localement, à chaque strate successive du mélange initial de poudres, l'énergie thermique suffisante pour amener le polymère à une température entraînant sa fusion. Les poudres non frittées assurent naturellement le support des couches suivantes. La plate-forme de travail mobile descend de l'épaisseur d'une couche, le déplacement de la pièce verticale étant assuré par un piston 6. Une nouvelle couche de poudre est ensuite étalée par le rouleau 3 et le cycle recommence pour construire la pièce couche par couche de bas en haut. A la place du rouleau 3, on pourrait également utiliser un autre système mécanique comme par exemple un racleur. Propriétés des pièces obtenues The process uses a manufacturing platform heated to a temperature close to the melting point of the polymer. The laser traces the layer-by-layer form and locally supplies, to each successive layer of the initial powder mixture, sufficient thermal energy to bring the polymer to a temperature causing it to melt. Unsintered powders naturally provide support for the following layers. The mobile work platform descends from the thickness of a layer, the displacement of the vertical part being provided by a piston 6. A new layer of powder is then spread by the roller 3 and the cycle starts again to build the part layer by layer from bottom to top. Instead of the roller 3, another mechanical system could be used, such as a scraper. Properties of the obtained parts
Les pièces obtenues après frittage présentent un retrait homogène de 2 ± 0,2 % selon les axes horizontaux x et y, et de 1,3 ± 0,2 % selon l'axe vertical z. La dureté Shore D moyenne est de 70±2. Elle est de 64±2 pour la même pièce sans pigment ou celle de l'exemple 5. La phosphorescence est homogène. The parts obtained after sintering have a homogeneous shrinkage of 2 ± 0.2% along the horizontal axes x and y, and 1.3 ± 0.2% along the vertical axis z. The average Shore D hardness is 70 ± 2. It is 64 ± 2 for the same piece without pigment or that of Example 5. The phosphorescence is homogeneous.
Exemple 2 : augmentation du taux de SrAI204 Example 2: Increase in SrAl 2 0 4
On a reproduit le mode opératoire de l'exemple 1, mais en utilisant un mélange de poudres constitué de 28 % en poids de pigment SrAI204 et de 72% en poids d'une poudre de polyamide qui est une poudre de Nylon 12. The procedure of Example 1 was repeated, but using a powder mixture consisting of 28% by weight of SrAl 2 O 4 pigment and 72% by weight of a polyamide powder which was a nylon 12 powder. .
Les pièces obtenues après frittage présentent un retrait homogène de The parts obtained after sintering have a homogeneous shrinkage of
2 ± 0,2 % selon les axes x et y et de 1,3 ± 0,2 % selon l'axe z. La dureté Shore D moyenne est améliorée par rapport à l'exemple 1, elle est de 74±2. La phosphorescence est homogène. 2 ± 0.2% along the x and y axes and 1.3 ± 0.2% along the z axis. The average Shore D hardness is improved compared to Example 1, it is 74 ± 2. The phosphorescence is homogeneous.
Exemple 3 : fabrication d'une pièce phosphorescente avec ZnS comme pigment Example 3: Manufacture of a phosphorescent part with ZnS as pigment
On a reproduit le mode opératoire de l'exemple 1, mais en utilisant un mélange de poudres constitué de 25 % en poids de pigment (ZnS :Cu) et de 75 % en poids d'une poudre de polyamide qui est une poudre de Nylon 12. The procedure of Example 1 was repeated, but using a mixture of powders consisting of 25% by weight of pigment (ZnS: Cu) and 75% by weight of a polyamide powder which is a nylon powder. 12.
Les pièces obtenues après frittage présentent un retrait homogène de 2 ± 0,2 % selon les axes x et y et de 1,3 ± 0,2 % selon l'axe z. La dureté Shore D moyenne est améliorée par rapport à la pièce sans pigment, elle est de 70±2. La phosphorescence est homogène. Exemple 4 : augmentation du taux de ZnS The pieces obtained after sintering have a homogeneous shrinkage of 2 ± 0.2% along the x and y axes and 1.3 ± 0.2% along the z axis. The average Shore D hardness is improved compared to the piece without pigment, it is 70 ± 2. The phosphorescence is homogeneous. Example 4: Increase in ZnS rate
On a reproduit le mode opératoire de l'exemple 1, mais en utilisant un mélange de poudres constitué par 45 % en poids de pigment (ZnS:Cu) et 55 % en poids d'une poudre de polyamide qui est une poudre de Nylon 12. The procedure of Example 1 was repeated, but using a mixture of powders consisting of 45% by weight of pigment (ZnS: Cu) and 55% by weight of a polyamide powder which is a nylon 12 powder. .
Les pièces obtenues après frittage présentent un retrait homogène de 2 ± 0,2 % selon les axes x et y et de 1,3 ± 0,2 % selon l'axe z. La dureté Shore D moyenne est améliorée par rapport à l'exemple 3, elle est de 74±2. La phosphorescence est homogène.  The pieces obtained after sintering have a homogeneous shrinkage of 2 ± 0.2% along the x and y axes and 1.3 ± 0.2% along the z axis. The average Shore D hardness is improved compared to Example 3, it is 74 ± 2. The phosphorescence is homogeneous.
Exemple 5 : pièce de forme très complexe recouverte avec de la peinture phosphorescente On a reproduit le mode opératoire de l'exemple 1, mais en utilisant une poudre constituée uniquement de polyamide Nylon 12. La pièce obtenue est ensuite recouverte d'une peinture phosphorescente à base de SrAI204. EXAMPLE 5 Very Complex Piece Part Coated with Phosphorescent Paint The procedure of Example 1 was repeated, but using a powder consisting solely of polyamide nylon 12. The part obtained is then covered with a phosphorescent paint with basis of SrAI 2 0 4 .
Les pièces obtenues après frittage présentent un retrait homogène de 2 ± 0,2 % selon les axes x et y et de 1,3 ± 0,2 % selon l'axe z. La dureté Shore D moyenne est de 64±2. La phosphorescence n'est pas homogène.  The pieces obtained after sintering have a homogeneous shrinkage of 2 ± 0.2% along the x and y axes and 1.3 ± 0.2% along the z axis. The average Shore D hardness is 64 ± 2. Phosphorescence is not homogeneous.

Claims

REVENDICATIONS
1. Utilisation d'un procédé de fabrication d'une pièce couche par couche, à partir de couches d'un mélange comprenant une poudre de polymère et une poudre d'un pigment phosphorescent, le poids du pigment n'excédant pas 90% du poids total du mélange, pour conférer de la phosphorescence à ladite pièce.  1. Use of a method for manufacturing a layer-by-layer part from layers of a mixture comprising a polymer powder and a powder of a phosphorescent pigment, the weight of the pigment not exceeding 90% of the total weight of the mixture, to impart phosphorescence to said piece.
2. Utilisation selon la revendication 1, pour conférer une phosphorescence homogène à ladite pièce. 2. Use according to claim 1, to give a homogeneous phosphorescence to said piece.
3. Utilisation selon la revendication 1 ou 2, caractérisée en ce que le procédé de fabrication couche par couche est le frittage sélectif par laser ou la stéréolithographie. 3. Use according to claim 1 or 2, characterized in that the layer-by-layer manufacturing process is selective laser sintering or stereolithography.
4. Utilisation selon l'une des revendications 1 à 3, caractérisée en ce que le polymère est un polymère organique thermoplastique choisi parmi les polyamides, les copolymères d'amide, les polyacétates, les polyéthylènes, le polyéthercétone. 4. Use according to one of claims 1 to 3, characterized in that the polymer is a thermoplastic organic polymer selected from polyamides, amide copolymers, polyacetates, polyethylenes, polyetherketone.
5. Utilisation selon l'une des revendications 1 à 4, caractérisée en ce que le pigment phosphorescent est à base de SrAI204 ou à base de ZnS. 5. Use according to one of claims 1 to 4, characterized in that the phosphorescent pigment is based on SrAI 2 0 4 or based on ZnS.
6. Utilisation selon l'une des revendications 1 à 5, caractérisée en ce que le mélange comprend de 10 à 91 % en poids de polymère. 6. Use according to one of claims 1 to 5, characterized in that the mixture comprises from 10 to 91% by weight of polymer.
7. Utilisation selon l'une des revendications 1 à 6, caractérisée en ce que le mélange comprend de 9 à 90 % en poids de pigment phosphorescent. 7. Use according to one of claims 1 to 6, characterized in that the mixture comprises from 9 to 90% by weight of phosphorescent pigment.
8. Utilisation selon l'une des revendications 1 à 7, caractérisée en ce que la granulométrie moyenne du pigment est comprise entre 5 et 120 pm. 8. Use according to one of claims 1 to 7, characterized in that the average particle size of the pigment is between 5 and 120 pm.
9. Utilisation selon l'une des revendications 1 à 8, caractérisée en ce que la granulométrie moyenne du polymère est comprise entre 1 et 120 pm. 9. Use according to one of claims 1 to 8, characterized in that the average particle size of the polymer is between 1 and 120 pm.
10. Procédé de fabrication d'une pièce phosphorescente, caractérisé en ce qu'il comprend une étape de fabrication couche par couche, à partir d'un mélange comprenant une poudre de polymère et une poudre d'un pigment phosphorescent à base de SrAI204 et/ou de ZnS, le poids du pigment n'excédant pas 90% du poids total du mélange, la granulométrie moyenne du pigment étant comprise entre 5 et 120 pm. 10. A method of manufacturing a phosphorescent part, characterized in that it comprises a step of manufacturing layer by layer, from a mixture comprising a polymer powder and a powder of a phosphorescent pigment based on SrAl 2 O 4 and / or ZnS, the weight of the pigment not exceeding 90% of the total weight of the mixture, the mean particle size of the pigment being included between 5 and 120 pm.
11. Procédé selon la revendication 10, caractérisé en ce que procédé est le frittage sélectif par laser. 11. The method of claim 10, characterized in that the method is selective sintering by laser.
12. Procédé selon la revendication 10 ou 11, caractérisé en ce que la granulométrie moyenne du pigment est comprise entre 10 et 80 pm. 12. The method of claim 10 or 11, characterized in that the average particle size of the pigment is between 10 and 80 pm.
13. Pièce phosphorescente, caractérisée en ce qu'elle est obtenue par un procédé selon l'une des revendications 10 à 12. 13. phosphorescent piece, characterized in that it is obtained by a method according to one of claims 10 to 12.
PCT/FR2012/051972 2011-09-07 2012-09-03 Use of a method of manufacturing a part layer by layer WO2013034841A1 (en)

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EP3306419B1 (en) * 2016-10-05 2019-11-27 The Swatch Group Research and Development Ltd Timepiece seal
EP4012507A1 (en) * 2020-12-11 2022-06-15 The Swatch Group Research and Development Ltd Phosphorescent timepiece component

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US6267911B1 (en) * 1997-11-07 2001-07-31 University Of Georgia Research Foundation, Inc. Phosphors with long-persistent green phosphorescence
US20040232583A1 (en) 2003-03-15 2004-11-25 Degusa Ag Process for producing three-dimensional objects by means of microwave radiation

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Publication number Priority date Publication date Assignee Title
US6267911B1 (en) * 1997-11-07 2001-07-31 University Of Georgia Research Foundation, Inc. Phosphors with long-persistent green phosphorescence
US20040232583A1 (en) 2003-03-15 2004-11-25 Degusa Ag Process for producing three-dimensional objects by means of microwave radiation

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