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    • 专利摘要:
    The invention relates to a poly (aryl-ether-ketone) (PAEK) powder which can be used several times in a method of building layer-by-layer objects by sintering caused by electromagnetic radiation, said powder characterized in that it is derived from a pre-heat treatment at a temperature between 260 and 290 ° C, preferably between 280 and 290 ° C, and in that it has a stable melting temperature, at construction temperature, and less than or equal to 330 ° C, preferably less than or equal to 320 ° C and even more preferably less than or equal to 310 ° C.
    公开号:FR3048430A1
    申请号:FR1651821
    申请日:2016-03-04
    公开日:2017-09-08
    发明作者:Benoit Brule；Jerome Pascal
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    POLY- (ARYL-ETHER-KETONE) POWDER (PAEK) SUITABLE FOR SEVERAL TIMES IN SINTERING PROCESSES
    TECHNICAL FIELD [0001] The invention relates to powders for use in layer-by-layer additive manufacturing processes of three-dimensional objects by sintering said powder caused by electromagnetic radiation. In particular, it relates to poly (aryl-ether-ketone) powders (PAEK) and their recyclability in such processes.
    The electromagnetic radiation may be a laser beam, in the case of laser sintering (still often referred to as "laser sintering" in English terminology), infrared radiation or UV radiation or any other source of radiation. The term "sintering" in the present description includes all these processes regardless of the type of radiation. Although in the following text reference is most often made to the laser sintering method, what is written for this method is of course valid for other sintering processes.
    [Prior Art] Poly (aryl-ether-ketones) are well known high performance engineering polymers. They are used for demanding applications in temperature and / or mechanical or chemical stresses. These polymers are found in fields as diverse as aeronautics and space, offshore drilling, automotive, rail, marine, wind, sports, building, electronics and implants. medical. They can be implemented by all thermoplastic processing technologies, such as molding, compression, extrusion, spinning, dusting or sintering prototyping.
    In the case of sintering the powder by electromagnetic radiation, a large part of the powder is not used during each construction, also called "run". Typically, about 85 to 90% by weight of the powder introduced into the sintering machine is not affected by the electromagnetic radiation. It therefore seems essential, for economic reasons, to be able to reuse this powder, that is to say to recycle it, during the following construction (s) (or "run (s)" ( s)).
    In general, during a construction by laser sintering, the PAEK powder is heated to a temperature T, called "construction temperature", of the order of 10 to 20 ° C (typically 15 ° C) in below its melting temperature Tf. However, during a construction by sintering, the surrounding powder, that is to say not touched by electromagnetic radiation, remains several hours, even several tens of hours depending on the complexity of the room to be built at this temperature which can cause an evolution of the structure of the constituent polymer of the powder with, for example, an increase in its molecular weight. This increase in molecular weight leads to an increase in viscosity which becomes a brake on the coalescence between the grains of powder during successive runs. This phenomenon is called "viscosity rise".
    Due to this change in structure, it becomes difficult if not impossible to recycle the powder because either it becomes impossible to sinter the powder, or the mechanical properties of the three-dimensional part, obtained by laser sintering of such a recycled powder , are diminished and insufficient by the presence of porosities in the sintered parts.
    [0007] There is currently on the market a poly (ether-ether-ketone) powder, PEEK, sold under the reference HP3 by the company EOS, which can be used in laser sintering. However, from the first run, the PEEK powder undergoes such a thermal degradation that it is not possible to reuse it for a second construction. Therefore, the manufacture of three-dimensional objects by sintering this powder is much too expensive and can not be considered on an industrial scale.
    US2013 / 0217838 proposes a solution to recycle a PAEK powder laser sintering. It more particularly describes the possibility of recycling a PEKK powder, provided that the construction temperature is substantially increased from 285 ° C. to 300 ° C. and that the power of the laser beam is increased each time the powder is recycled during runs. successive. This document indeed describes that the PEKK powder used is not stable in temperature and that its melting temperature increases after its first use in a sintering process. In order to counter this instability of the powder, the parameters of the sintering machine are modified. The power of the laser beam, in particular, is increased with each run. The fact of having to change these sintering parameters with each run slows down and makes industrial production more difficult. In addition, it appears difficult to mix non-recycled powder with recycled powder, because the construction parameters are then complex to adjust. Finally, the fact of having to modify the parameters at each run, and in particular to increase the power of the laser, causes a degradation of the polymer powder, so that the number of recycling of the powder is still too limited and it would be economically advantageous to to be able to recycle it further.
    [Technical problem] [0009] The object of the invention is therefore to remedy at least one of the disadvantages of the prior art. In particular, the object of the invention is to propose a PAEK powder that can be used several times in successive sintering processes, the parameters of which remain unchanged, and which makes it possible to obtain three-dimensional articles having satisfactory mechanical properties.
    The invention further aims to provide a method of constructing a three-dimensional layer-by-layer object by sintering powder caused by electromagnetic radiation, using such a powder.
    The invention finally aims to propose a three-dimensional article obtained by sintering such a layer-by-layer powder using an electromagnetic radiation, said three-dimensional article having satisfactory and substantially constant mechanical properties. that is the number of uses of the powder.
    BRIEF DESCRIPTION OF THE INVENTION [0012] The invention relates to a poly (aryl ether ketone) (PAEK) powder which can be used several times in a method of building layer-by-layer objects. by sintering caused by electromagnetic radiation, said powder being characterized in that it is derived from a pre-heat treatment at a temperature between 260 and 290 ° C, preferably between 280 and 290 ° C, and that it has a stable melting temperature, at the temperature of construction, and less than or equal to 330 ° C, preferably less than or equal to 320 ° C and even more preferably less than or equal to 310 ° C.
    Such a powder has the advantage of not suffering (or little) rise in viscosity after sintering and can thus be used several times, and much more than twice, in successive methods of construction by sintering, without changing the parameters, while allowing to obtain three-dimensional articles having satisfactory and substantially constant mechanical properties.
    According to other optional features of the powder: - its preliminary heat treatment is carried out for a period of between 5 min and 120 min, preferably between 5 min and 60 min and more preferably between 5 min and 30 min ; the PAEK powder comprises a mixture of several polymers belonging to the PAEK family, whose melting temperature Tf is less than or equal to 330 ° C., preferably less than or equal to 320 ° C. and even more preferably lower or equal to 310 ° C., the PAEK powder comprises at least one polyether-ketone-ketone (PEKK) powder which represents more than 60% by weight, preferably more than 70% by weight of the powder, including the terminal. the powder is a polyether-ketone-ketone powder (PEKK); the PEKK powder has a mass percentage of terephthalic units relative to the sum of the terephthalic and isophthalic units of between 55 and 65%; - The powder comprises a mixture of recycled powders or not, said recycled powders having been used an identical and / or different number of cycles.
    The invention also relates to a use of the powder as described above, in a method of building a layer-by-layer object by laser sintering, said powder being reusable in several successive constructions.
    The invention further relates to a method of constructing a three-dimensional layer-by-layer object by sintering powder caused by electromagnetic radiation, characterized in that the powder used is in accordance with the powder described above. .
    Finally, the invention relates to a three-dimensional article obtained by sintering a layer-by-layer powder using an electromagnetic radiation, said powder being characterized in that it conforms to the powder described herein. -above.
    Other advantages and features of the invention will appear on reading the following description given by way of illustrative and non-limiting example.
    [Description of the Invention] [0019] In the preamble, it is specified that the expression "included (e) between" used in the context of this description should be understood as including the boundaries cited.
    The term "construction temperature" refers to the temperature at which the powder bed, a constituent layer of a three-dimensional object in construction, is heated during the sintering process layer-by-layer of the powder. This construction temperature is below the melting temperature of the powder of 40 ° C, preferably 30 ° C, more preferably 20 ° C.
    The poly (aryl ether ketones) (PAEK) contain the following units of formulas: (- Ar - X -) and (- Ari - Y -) in which: - Ar and Ari each denote an aromatic radical divalent; Ar and Ar may be chosen, preferably, from 1,3-phenylene, 1,4-phenylene, 4,4'-biphenylene, 1,4-naphthylene, 1,5-naphthylene and 2, 6-naphthylene; X denotes an electron-withdrawing group; it can be chosen, preferably, from the carbonyl group and the sulphonyl group; Y denotes a group chosen from an oxygen atom, a sulfur atom, an alkylene group, such as -CH 2 - and isopropylidene.
    In these units X and Y, at least 50%, preferably at least 70% and more particularly, at least 80% of the X groups are a carbonyl group, and at least 50%, preferably at least 70% and more particularly at least 80% of the Y groups represent an oxygen atom. According to a preferred embodiment, 100% of the X groups denote a carbonyl group and 100% of the Y groups represent an oxygen atom.
    More preferably, the polyarylene ether ketone (PAEK) may be chosen from: a polyetherketone ketone, also called PEKK, comprising units of formula IA, of formula IB and their mixture:
    Formula I A
    Formula I B is a polyether ether ketone, also called PEEK, comprising units of formula II:
    Formula II
    The sequences can be totally para (Formula II). In the same way one can introduce, partially or totally, sequences mta in these structures at the level of the ethers and the ketones according to the two examples of formulas III and IV below:
    Formula III
    Or :
    Form IV
    Or sequences in ortho according to the formula V:
    Formula V a polyether ketone, also called PEK, comprising units of formula VI:
    Form VI
    In the same way, the sequence can be totally para but one can also introduce meta sequences partially or totally (formulas VII and VIII):
    Form VII
    Or
    - -y
    Formula VIII a polyether-ether-ketone-ketone, also called PEEKK, comprising units of formulas IX:
    Form IX
    In the same way we can introduce meta sequences in these structures at the level of ethers and ketones. a poly-ether-ether-ether-ketone, also called PEEEK, comprising units of formulas X:
    Formula X
    In the same way we can introduce meta sequences in these structures at the level of ethers and ketones but also biphenolic chains according to formula XI:
    Form XI
    Other arrangements of the carbonyl group and the oxygen atom are also possible.
    Among the PAEK described above, some have a melting temperature Tf greater than 330 ° C. However, it is well known to those skilled in the art that the melting temperature can be lowered by introducing comonomers into the formulas. By way of example, mention may be made of a PEEK-based copolymer with addition of biphenol-type comonomers (formula XI).
    Preferably, the PAEKs used in the invention are chosen from PEKK, PEEK-based copolymers and PEK-based copolymers.
    Advantageously, the PAEK powder according to the invention intended to be used in a method of additive construction of objects, layer-by-layer, by sintering the powder caused by electromagnetic radiation, is derived from a pre-heat treatment carried out at a temperature of between 260 and 290, preferably between 280 and 290 ° C.
    The PAEK polymer is indeed not used as such, directly after its synthesis, in a layer-by-layer construction process by sintering. It is first converted into powder form, by grinding, to modify the particle size of the polymer and to obtain a powder having a suitable particle size, known to those skilled in the art, compatible with the laser sintering process. This grinding step may be followed by other treatments, such as for example one or more additions of additive (s), filler (s) or fibers in the powder.
    Advantageously, the heat treatment prior to the sintering step, performed after the grinding step, allows to modify the thermal signature of the polymer without changing its particle size. In PEKK, the constituent polymer material of the initial powder, obtained directly at the end of the synthesis, has two melting peaks, called high temperature and low temperature melting peaks. The prior heat treatment makes it possible to eliminate the melting peak at low temperature and to stabilize the crystalline morphology of the polymer, without modifying its high melting point.
    With this heat treatment, the powder according to the invention has a stable melting temperature at the building temperature. For the purposes of the invention, a stable melting temperature Tf means that the melting temperature does not increase by more than 3 ° C. after each laser sintering process, and preferably it does not increase by more than 2 ° C. C and even more preferably, it does not increase more than 1 ° C. Preferably, the melting temperature of the polymer powder is less than or equal to 330 ° C, more preferably less than or equal to 320 ° C, and even more preferably less than or equal to 310 ° C.
    Such a powder has the advantage of being thermally stable during a construction process by sintering and does not evolve. Its molecular weight remains stable and the phenomenon of viscosity rise, due to the increase in molecular weight, which has been observed until now does not appear or little.
    Preferably, the heat treatment of the powder is carried out for a period of between 5 min and 120 min, preferably between 5 min and 60 min and more preferably between 5 min and 30 min, [0033] layer-by-layer construction process by sintering the powder by means of electromagnetic radiation is then performed at a construction temperature of the same order of magnitude as that of the pre-heat treatment. This construction temperature is below the melting temperature of the powder of 40 ° C, preferably 30 ° C and more preferably 20 ° C. Preferably, the building temperature is less than 290 ° C.
    The PAEK powder may comprise a mixture of several polymers belonging to the family of PAEK, and whose melting temperature Tf is less than 330 ° C, preferably less than or equal to 320 ° C, and even more preferred less than or equal to 310 ° C.
    Preferably, the PAEK powder comprises at least one polyether-ketone-ketone (PEKK) powder which represents more than 60%, preferably more than 70% by weight of the powder, including the terminal. The remaining 30 to 40% by weight may for example consist of other polymers belonging to the PAEK family, and whose melting temperature is less than or equal to 330 ° C., and / or by fillers and / or by fibers, such as carbon fibers, glass fibers for example, by glass beads, by mineral fillers, or by carbon blacks, graphites, graphenes, carbon nanotubes.
    [0036] More preferably, the PAEK powder is a PEKK powder. Advantageously, this PEKK powder has a mass percentage of terephthalic units relative to the sum of the terephthalic and isophthalic units of between 55 and 65% and preferably, this ratio is 60%.
    Due to this thermal stability of the powder, it can be used a large number of times in successive processes for the construction of layer-by-layer objects, by sintering the powder by means of a laser beam. example.
    In addition, because of this stability of the powder, the parameters of the construction machine by sintering remain unchanged regardless of the number of subsequent uses of the powder. As a result, the production of objects by laser sintering becomes more productive. The recyclability of the powder being improved the sintering of PAEK powder becomes economically interesting and industrially possible.
    Finally, because the sintering parameters remain unchanged, it becomes possible and easy to use a powder comprising a mixture of different powders recycled or not, the recycled powders may also have been used an identical number of cycles and / or different.
    The powder according to the invention is therefore very interesting economically since it can be recycled several times in a sintering process, while ensuring the same settings of the construction machine.
    Finally, the invention relates to a three-dimensional article, obtained by sintering the powder which has just been described, layer-by-layer, using an electromagnetic radiation, of the laser type, for example. The object obtained has satisfactory and constant mechanical properties regardless of the number of uses of the powder.
    Examples: 1. Evolution of PAEK powders after a first sintering Two PEKK powders are compared: a reference PEKK powder comprising 60% of terephthalic units and 40% of isophthalic units and which have not undergone treatment prior thermal, and a PEKK powder according to the invention, comprising 60% of terephthalic units and 40% of isophthalic units.
    After synthesis of the two PEKK polymers, they are ground into the powder state. Only the powder according to the invention undergoes a preliminary heat treatment of 120 minutes at 285 ° C.
    The viscosity in solution in 96% sulfuric acid of the reference powder is then measured at 0.87dl / g. The viscosity of the powder according to the invention in solution in 96% sulfuric acid is measured at 0.85 dl / g. The viscosities are measured at 25 ° C. using a Ubbelohde tube viscometer.
    The two powders are then placed each in a tube under nitrogen flushing and heated at 285 ° C for 24 hours. Each powder is then again analyzed in solution viscosity and a viscosity of 0.90 dl / g is found for the reference powder and a viscosity of 0.85 dl / g for the powder according to the invention. As a result, the viscosity of the reference powder increases by more than 3% after 24 hours at 285 ° C., whereas the viscosity of the powder according to the invention remains constant. The uncertainty on the measurement corresponds to 0.01 dl / g.
    Table I
    The PEKK powder according to the invention has an inherent viscosity which does not change significantly (evolution between 0 and 1% which corresponds to the uncertainty on the measurement), unlike the reference powder for which the inherent viscosity increases significantly with an increase greater than 3%.
    2. Recyclability after sintering at a construction temperature of Tf-15 ° C
    The two powders of Example 1 and a PEEK powder sold by the company EOS under the reference HP3, were compared after a first sintering at a temperature of 15 ° C below their respective melting temperatures. , and their recyclability at the end of this sintering was evaluated.
    The PEEK HP3 powder has a melting temperature of 372 ° C. The reference PEKK powder has, before the first sintering, a melting temperature Tf1 of 300 ° C., but this temperature changes and increases after the first sintering, by about fifteen degrees. The PEKK powder according to the invention, for its part, has an average melting point of 300 ° C. and remains constant at the end of the sintering process. It is called "average melting temperature" because, even if it does not evolve, it can be slightly different depending on the batch of powder and varies between 297 and 303 ° C.
    The measurement of the melting temperature is carried out by differential scanning calorimetry measurement DSC (acronym for Differential Scanning Calorimetry) according to the IS011357-3 standard.
    Those skilled in the art know that for a PAEK powder, it is usual to heat the construction chamber to a construction temperature of 10 to 20 ° C (typically 15 ° C) below the melting temperature. of the polymer material constituting the powder in order to be able to produce a three-dimensional object in laser sintering with good sintering performance and mechanical properties of the final object obtained.
    Laser sintering tests were performed on a DTM Sinter station 2500 device modified to be able to work at high temperature (that is to say up to 300 ° C). The powder not subjected to the laser beam, and therefore not sintered, remaining in the construction tank, also called "powder to recycle", was recovered.
    The initial powder, that is to say before its first use in the laser sintering machine and the powder to be recycled were compared by dissolution. For this, about 30 mg of powder is dissolved in 1 ml of 4-chlorophenol at 150 ° C for 24 hours. After cooling the solution to room temperature, 14 ml of Hexafluoroisopropanol (HFIP) are added. The solution is filtered on a syringe filter brand Acrodisc with a polytetrafluoroethylene membrane (PTFE) with a diameter of 25mm and a porosity of 0.2pm.
    Table II
    The results, collected in Table II above, demonstrate that when the construction temperature is set to 15 ° C below the melting temperature, the PEEK HP3 powder, once used, becomes insoluble with more of 99% by weight of insoluble particles, which means that it has crosslinked, its molecular weight has increased and the polymer has changed structure.
    The other two PEKK powders are soluble, with less than 5% by weight of insoluble particles, which means that they can be reused.
    However, the reference PEKK powder, after the first sintering, has a second melting temperature Tf2 greater than the first of fifteen degrees. This increase in the melting temperature results, in order to be able to recycle the powder in a laser sintering process, to modify the sintering parameters, and in particular the construction temperature, but also the power of the laser beam.
    The PEKK powder according to the invention has a constant melting temperature during the laser sintering process. It thus makes it possible to obtain one or more other sintered pieces without changing the parameters of the sintering apparatus. 3. Sintering ability at constant temperature of construction The three powders HP3, PEKK reference and PEKK according to the invention are again compared for their sinterability at a fixed construction temperature, constant regardless of the number of sintering cycles.
    To be able to recycle the powder, the experiment was conducted by fixing the construction temperature at 285 ° C., in order to avoid thermal degradation of the powder and to be able to recycle it into subsequent constructions by laser sintering. The sintering is carried out under the same experimental conditions, in particular at a fixed construction temperature and for a suitable and constant laser power.
    The initial powder, that is to say before the first sintering, was compared to the powder recovered in the construction tank after sintering (= powder to recycle) and a powder recycled once. For each of these powders, the mechanical properties of the sintered test pieces were measured and compared, in particular the tensile modulus and the elongation at break.
    The results of these comparisons are summarized in Table NI below.
    NI Table
    It turns out that at the construction temperature of 285 ° C, this temperature being much lower than the melting temperature of 372 ° C of PEEK HP3 powder, HP3 powder is not degraded and can to be recycled. However, at this temperature, the powder is not properly sintered and the three-dimensional object obtained does not have good mechanical properties, it does not pass the tests.
    The reference PEKK is also recyclable and the object obtained after the first sintering has good mechanical properties. On the other hand, if the same construction temperature is left at 285 ° C for a second test, then, in this case, the powder is again recyclable but the three-dimensional object obtained has mechanical properties whose performance is significantly reduced.
    In this case, only the PEKK powder according to the invention makes it possible to obtain sintered test pieces with good mechanical properties, regardless of the number of sintering cycles and this, with sintering parameters unchanged, as well. well in construction temperature than laser beam power. 4. Successive sintering tests of different powders under conventional sintering conditions Table IV below collates the parameters of the laser sintering machine, in the context of successive constructions, made under conventional conditions, with the three powders of HP3, reference PEKK and PEKK according to the invention, to obtain sintered parts having satisfactory mechanical properties. The number of constructions (tests) indicated in the table is 4, but for the powder according to the invention, sintered parts could be obtained with recycled powder a greater number of times without observing a significant decrease in properties. mechanical.
    Table IV
    This table shows that the PEKK powder according to the invention, used several times in succession to make layer-by-layer three-dimensional objects, by laser sintering of the powder, makes it possible to obtain objects having properties mechanical satisfactory and stable regardless of the number of recycling of the powder. In addition, the construction parameters of the laser sintering machine remain unchanged regardless of the number of recycling of the powder.
    It has been observed, with the reference PEKK powder, according to the prior art, that the mechanical properties of the three-dimensional object obtained after 2 cycles are affected and begin to decrease. It therefore becomes very difficult to recycle this powder in sintering processes beyond 3 or 4 cycles.
    The PAEK powder according to the invention which has just been described, with a stable melting temperature of less than 330 ° C. and preferably less than or equal to 310 ° C., has improved recyclability, so that it becomes economically very interesting. It makes it possible to construct three-dimensional objects by sintering, without changing the parameters of the sintering process, so that it can significantly improve productivity. Finally, the three-dimensional objects obtained have satisfactory and constant mechanical properties regardless of the number of cycles.
    权利要求:
    Claims (10)
    [1" id="c-fr-0001]
    Claims:
    Poly (aryl-ether-ketone) powder (PAEK), which can be used several times in a method of building layer-by-layer objects by sintering caused by electromagnetic radiation, said powder being characterized in that it is derived from a heat treatment preliminarily at a temperature of between 260 and 290 ° C, preferably between 280 and 290 ° C, and in that it has a stable melting temperature, at the temperature of construction, and less than or equal to 330 ° C, preferably less than or equal to 320 ° C and even more preferably less than or equal to 310 ° C.
    [2" id="c-fr-0002]
    2. Powder according to claim 1, characterized in that its preliminary heat treatment is carried out for a period of between 5 min and 120 min, preferably between 5 min and 60 min and more preferably between 5 min and 30 min.
    [3" id="c-fr-0003]
    3. Powder according to any one of claims 1 or 2, characterized in that it comprises a mixture of several polymers belonging to the family of PAEK, whose melting temperature Tf is less than or equal to 330 ° C, preferably less than or equal to 320 ° C and even more preferably less than or equal to 310 ° C.
    [4" id="c-fr-0004]
    4. Powder according to any one of claims 1 to 3, characterized in that it comprises at least one polyether-ketone-ketone (PEKK) powder which represents more than 60% by mass, preferably more than 70% by mass of the powder, including the terminal.
    [5" id="c-fr-0005]
    5. Powder according to any one of claims 1 or 2, characterized in that the powder is a polyether-ketone-ketone powder (PEKK).
    [6" id="c-fr-0006]
    6. Powder according to claim 4 or 5, characterized in that the PEKK powder has a mass percentage of terephthalic units relative to the sum of the terephthalic and isophthalic units of between 55 and 65%.
    [7" id="c-fr-0007]
    7. Powder according to one of claims 1 to 6 characterized in that it comprises a mixture of recycled powders or not, said recycled powders having been used an identical and / or different number of cycles.
    [8" id="c-fr-0008]
    8. Use of the powder according to one of claims 1 to 7, in a method of building layer-by-layer object by laser sintering, said powder being reusable in several successive constructions.
    [9" id="c-fr-0009]
    9. A method of constructing a three-dimensional layer-by-layer object by sintering powder caused by electromagnetic radiation, characterized in that the powder used is according to one of claims 1 to 7.
    [10" id="c-fr-0010]
    10. Three-dimensional article obtained by sintering a layer-by-layer powder using electromagnetic radiation, said powder being characterized in that it conforms to one of claims 1 to 7.
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    EP2791209A1|2011-12-12|2014-10-22|Advanced Laser Materials LLC|Method and system for laser sintering with pretreated material|
    WO2014191675A1|2013-05-30|2014-12-04|Arkema France|Method for the thermal treatment of poly-arylene ether ketone ketone powders suitable for laser sintering|
    WO2014191674A1|2013-05-30|2014-12-04|Arkema France|Composition of poly-arylene ether ketone ketone powders suitable for laser sintering|
    FR3088647B1|2018-11-15|2021-02-26|Arkema France|REUSABLE POLYPOWDER FOR SINTERING PROCESS|
    FR3093666B1|2019-03-15|2022-01-14|Arkema France|Process for the manufacture by sintering of a powder based on partly recycled poly-aryl-ether-ketone|
    FR3102182A1|2019-10-18|2021-04-23|Arkema France|Powder based on PAEK , use in construction processes by sintering, corresponding article.|
    EP3825345A1|2019-11-19|2021-05-26|Arkema France|Improved powder for additive manufacturing|
    法律状态:
    2017-02-13| PLFP| Fee payment|Year of fee payment: 2 |
    2017-09-08| PLSC| Publication of the preliminary search report|Effective date: 20170908 |
    2018-02-23| PLFP| Fee payment|Year of fee payment: 3 |
    2019-02-13| PLFP| Fee payment|Year of fee payment: 4 |
    2020-02-14| PLFP| Fee payment|Year of fee payment: 5 |
    2021-02-10| PLFP| Fee payment|Year of fee payment: 6 |
    2022-02-09| PLFP| Fee payment|Year of fee payment: 7 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1651821A|FR3048430B1|2016-03-04|2016-03-04|POLY-POWDERSUITABLE FOR SEVERAL TIMES IN SINTERING PROCESSES|
    FR1651821|2016-03-04|FR1651821A| FR3048430B1|2016-03-04|2016-03-04|POLY-POWDERSUITABLE FOR SEVERAL TIMES IN SINTERING PROCESSES|
    PCT/FR2017/050439| WO2017149233A1|2016-03-04|2017-02-28|Poly-powder for using multiple times in sintering methods|
    US16/080,261| US20210171709A2|2016-03-04|2017-02-28|Polypowder suitable for multiple use in sintering methods|
    EP17713718.9A| EP3423510A1|2016-03-04|2017-02-28|Poly-powder for using multiple times in sintering methods|
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