(19)
(11)EP 3 344 442 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
29.04.2020 Bulletin 2020/18

(21)Application number: 16770818.9

(22)Date of filing:  02.09.2016
(51)International Patent Classification (IPC): 
B29C 67/00(2017.01)
C08J 3/28(2006.01)
C08J 3/12(2006.01)
C08K 3/36(2006.01)
(86)International application number:
PCT/US2016/050052
(87)International publication number:
WO 2017/040893 (09.03.2017 Gazette  2017/10)

(54)

POWDER COMPOSITIONS, METHOD OF PREPARING ARTICLES AND COATINGS FROM THE POWDER COMPOSITIONS, AND ARTICLES PREPARED THEREFROM

PULVERZUSAMMENSETZUNGEN, VERFAHREN ZUR HERSTELLUNG VON ARTIKELN UND BESCHICHTUNGEN AUS DEN PULVERZUSAMMENSETZUNGEN UND DARAUS HERGESTELLTE ARTIKEL

COMPOSITIONS DE POUDRE, PROCÉDÉ DE PRÉPARATION D'ARTICLES ET DE REVÊTEMENTS À PARTIR DES COMPOSITIONS DE POUDRE, ET ARTICLES AINSI PRÉPARÉS


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 04.09.2015 US 201562214386 P

(43)Date of publication of application:
11.07.2018 Bulletin 2018/28

(73)Proprietor: SABIC Global Technologies B.V.
4612 PX Bergen op Zoom (NL)

(72)Inventor:
  • PRICE, Brian
    Mount Vernon, IN 47620-9367 (US)

(74)Representative: Office Freylinger 
P.O. Box 48
8001 Strassen
8001 Strassen (LU)


(56)References cited: : 
EP-A2- 0 154 189
WO-A2-2007/079270
US-A- 6 136 948
US-A1- 2003 130 418
WO-A1-2015/157148
US-A- 5 185 108
US-A1- 2003 092 837
  
  • LI E K H ET AL: "Experimental size ratio and compositional effects on the packing and hot isostatic pressing of spherical powders", MATERIALS SCIENCE AND ENGINEERING A: STRUCTURAL MATERIALS: PROPERTIES, MICROSTRUCTURES AND PROCESSING, ELSEVIER BV, NL, vol. 157, no. 2, 1 October 1992 (1992-10-01), pages 217-224, XP024356289, ISSN: 0921-5093, DOI: 10.1016/0921-5093(92)90028-Y [retrieved on 1992-10-01]
  
Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


Description

BACKGROUND



[0001] A number of manufacturing processes make use of particulate thermoplastic polymer compositions, commonly known in the art as "powder compositions." Additive manufacturing (AM, also known as "three-dimensional" or "3D" printing) is a process for the manufacture of three-dimensional objects by formation of multiple fused layers. AM methods using powder compositions include powder bed fusing. In powder bed fusing, thermal energy selectively fuses regions of a powder bed. In particular, selective laser sintering (SLS) is a powder bed fusion process using one or more lasers to fuse powdered thermoplastic polymers into the desired three-dimensional shape. In powder coating, the powder composition is applied to a surface, for example electrostatically, and then heated, allowing the particles to coalesce and form a film. Powder compositions have also been compression molded to form articles.

[0002] Despite their long use, there remains a need in the art for optimized powder properties, in particular optimized shape and size of the polymer particulates. Ease of particle handling has driven practitioners to larger particle sizes. However, larger particle sizes coalesce more slowly during the sintering process. Particle size can also affect the porosity of the final product. In the manufacturing of parts by the sintering of particles, the mechanical properties of the final article can be deficient compared to the same article formed of the same material by methods such as injection molding. This discrepancy in properties is typically attributable to the increased porosity of the sintered part resulting from suboptimal packing and coalescence of the particles. US6136948 discloses a method of producing a three-dimensional object with a lower porosity comprising powder fusing or compression molding a powder composition comprising polyamide particles having a two-tier particle size distribution.

[0003] It can further be difficult to use amorphous thermoplastic polymers in these processes, particularly in powder bed fusing, because the amorphous polymers do not have a sharp melting point. This property causes the applied thermal energy source (e.g., a laser beam) to be dissipated into the regions surrounding the location where the energy beam strikes the bed. This undesired dissipation of thermal energy can cause unstable processing as well as poor feature resolution in the intended three-dimensional articles being produced.

[0004] Therefore, there is a need in the art for powder compositions having optimized size and shape characteristics. It would be a further advantage if such compositions provided improved processing of amorphous polymers.

BRIEF DESCRIPTION



[0005] In an embodiment, a powder composition comprises a plurality of thermoplastic particles characterized by a bimodal particle size distribution comprising, based on the total weight of the particles, 85 to 94 weight percent (wt%), preferably 87 to 91 wt%, more preferably 89 wt% of the particles having a first D50 of 1 nm to 500 micrometers; and 6 to 15 wt%, preferably 9 to 13 wt%, more preferably 11 wt% of the particles having a D50 that is 0.414 times the first D50; wherein the thermoplastic polymer is a polycarbonate, a polyetherimide, a polyimide, a polysulfone, a polyethersulfone, a polyarylene ether, a polyetherether ketone, a polyamide or a combination comprising at least one of the foregoing.

[0006] In another embodiment, a powder composition comprises a plurality of thermoplastic particles characterized by a bimodal particle size distribution comprising, based on the total weight of the particles, 67 to 77 wt%, preferably 70 to 74 wt%, more preferably 72 wt% of the particles having a first D50 of 1 nm to 500 micrometers; and 23 to 33 wt%, preferably 26 to 30 wt%, more preferably 28 wt% of the particles having a second D50 that is 0.732 times the first D50; wherein the thermoplastic polymer is a polycarbonate, a polyetherimide, a polyimide, a polysulfone, a polyethersulfone, a polyarylene ether, a polyetherether ketone, a polyamide or a combination comprising at least one of the foregoing.

[0007] In another embodiment, a powder composition comprises a plurality of thermoplastic particles characterized by a trimodal particle size distribution comprising, based on the total weight of the particles, 66 to 76 wt%, preferably 69 to 73 wt%, more preferably 71 wt% of the particles having a first D50 of 1 nm to 500 micrometers; 23 to 33 wt%, preferably 26 to 30 wt%, more preferably 28 wt% of the particles having a second D50 that is 0.732 times the first D50; and 0.5 to 5 wt%, preferably 1 to 3 wt%, more preferably 1 wt% of the particles having a third D50 that is 0.268 times the first D50; wherein the thermoplastic polymer is a polycarbonate, a polyetherimide, a polyimide, a polysulfone, a polyethersulfone, a polyarylene ether, a polyetherether ketone, a polyamide or a combination comprising at least one of the foregoing.

[0008] A method of preparing a three-dimensional article comprises powder bed fusing the powder composition to form a three-dimensional article.

[0009] A three-dimensional article prepared by the above method is also disclosed.

[0010] A method of preparing a powder coating comprises applying a powder coating layer comprising the powder composition to a substrate; and consolidating the powder coating layer to form the powder coating.

[0011] A powder coated article made by the above method is also disclosed.

[0012] A method of preparing a three-dimensional article comprises compression molding the powder composition to form the three-dimensional article.

[0013] The above described and other features are exemplified by the following figures and detailed description.

BRIEF DESCRIPTION OF THE DRAWINGS



[0014] The following figures are of exemplary embodiments.

FIG. 1 shows a cubic lattice showing three sizes of spheres that can fit in the lattice simultaneously.

FIG. 2 shows a face-centered cubic lattice showing two sizes of spheres that can fit in the lattice simultaneously.

FIG. 3 shows a particle size distribution of a polyetherimide powder sample.

FIG. 4 shows an overlay of the particle size distributions of the main particle size distribution, the 0.414 size distribution, and the combined distribution.

FIG. 5 shows the flowability as a function of flow promoter content (in terms of relative surface area coverage (SAC)) for a bulk powder and an optimized powder.


DETAILED DESCRIPTION



[0015] Disclosed herein are particulate thermoplastic compositions (also referred to herein as "powder compositions") having optimized particle size and particle size distribution. The present inventors have unexpectedly found that powder compositions having a specified particle size and particle size distribution can advantageously be used in various additive manufacturing processes to provide three-dimensional articles with decreased void volume to due optimal particle packing. Particularly, the powder compositions can have multimodal particle size distributions that can fill space in an optimal manner, so as to provide a three dimensional article having no unintended voids. Articles prepared from powder compositions having optimized particle size and particle size distribution can have improved mechanical properties due to the decreased porosity that arises from the optimal packing and coalescence of the particles.

[0016] An optimized particle size distribution of the thermoplastic particles of a powder composition can be achieved by reducing the volume that is not occupied by the particles when packed. Optimized particle size distributions can be determined using simple models of cubic- and face-centered cubic lattices. An exemplary cubic lattice showing three sizes of spheres that can fit in the lattice simultaneously is shown in FIG. 1. On a cubic lattice, as shown in FIG. 1, the largest particle size determines the cube. The size of the largest particles can be referred to as D1. Using a single particle size, the resulting cube has a porosity of 48% (i.e., 52% of the total volume of the cube is filled by the single size particles). The next largest sphere (having a size referred to as D2) that can fit inside the remaining space of the cube created by the largest spheres can be defined by D2=(31/2-1)D1. Thus in some embodiments, when particles having a size D2 are included in the cube, the porosity can be decreased to 27% (i.e., 73% of the total volume of the cube is filled by the particles having a bimodal distribution comprising D1 and D2). In another embodiment, particles having a third size D3, wherein D3 < D2 < D1, can be added to the cube to further decrease the porosity. D3 can be defined by D3=(2-31/2)D1. Thus in some embodiments, when particles having a size D3 are included in the cube, the porosity can be decreased to 24% (i.e., 76% of the total volume of the cube is filled by the particles comprising a trimodal distribution comprising D1, D2, and D3).

[0017] An exemplary face-centered cubic lattice is shown in FIG. 2. Using a similar procedure as described above, the two largest particles sizes (D1 and D2) that can simultaneously fit in the face-centered cubic lattice can be determined. In an embodiment, the relationship between D1 and D2 can be defined by D2=(21/2-1)D1.

[0018] Accordingly, one aspect of the present disclosure is a powder composition comprising a plurality of thermoplastic particles characterized by a multimodal distribution, preferably a bimodal distribution or a trimodal distribution. In an embodiment, a powder composition comprises a plurality of thermoplastic particles characterized by a bimodal particle size distribution comprising, based on the total weight of the particles, 85 to 94 wt%, preferably 87 to 91 wt%, more preferably 89 wt% of the particles having a first D50 of 1 nm to 500 micrometers; and 6 to 15 wt%, preferably 9 to 13 wt%, more preferably 11 wt% of the particles having a D50 that is 0.414 times the first D50. As used herein, D50 refers to the particle diameter of the powder where 50 wt% of the particles in the total distribution of the referenced sample have the noted particle diameter or smaller. Particle sizes can be measured by any suitable methods that are generally known to measure particle size by diameter. In some embodiments, the particle size is determined by laser diffraction. For example, particle size can be determined using a diffractometer such as the Mastersizer 3000 from Malvern.

[0019] In an embodiment, a powder composition comprises a plurality of thermoplastic particles characterized by a bimodal particle size distribution comprising, based on the total weight of the particles, 67 to 77 wt%, preferably 70 to 74 wt%, more preferably 72 wt% of the particles having a first D50 of 1 nm to 500 micrometers; and 23 to 33 wt%, preferably 26 to 30 wt%, more preferably 28 wt% of the particles having a second D50 that is 0.7732 times the first D50.

[0020] In another embodiment, a powder composition comprises a plurality of thermoplastic particles characterized by a trimodal particle size distribution comprising, based on the total weight of the particles, 66 to 76 wt%, preferably 69 to 73 wt%, more preferably 71 wt% of the particles having a first D50 of 1 nm to 500 micrometers; 23 to 33 wt%, preferably 26 to 30 wt%, more preferably 28 wt% of the particles having a second D50 that is 0.7732 times the first D50; and 0.5 to 5 wt%, preferably 1 to 3 wt%, more preferably 1 wt% of the particles having a third D50 that is 0.268 times the first D50.

[0021] In some embodiments, the first D50 is 15 nm to 100 µm, more preferably 25 nm to 50 µm. In some embodiments, the first D50 is 100 nm to 50 µm, preferably 150 nm to 25 µm, more preferably 200 nm to 10 µm.

[0022] The powder compositions having the above-described particle size distributions comprise thermoplastic particles comprising a thermoplastic polymer. The particles can generally be of any shape suitable for a desired application. In some embodiments, the particles are preferably spherical particles, and more preferably are spherical particles having a sphericity of 0.9 to 1. Alternatively, or in addition, the thermoplastic particles can each have a minimum and a maximum radius of within 10%, preferably within 5%.

[0023] As used herein, the term "thermoplastic" refers to a material that is plastic or deformable, melts to a liquid when heated, and freezes to a brittle, glassy state when cooled sufficiently. Thermoplastics are typically high molecular weight polymers. The thermoplastic polymer can be crystalline, semi-crystalline, or amorphous. The terms "amorphous" and "crystalline" as used herein are accorded their usual meanings in the polymer art. For example, in an amorphous polymer the molecules can be oriented randomly and can be intertwined, and the polymer can have a glasslike, transparent appearance. In crystalline polymers, the polymer molecules can be aligned together in ordered regions. In the polymer art, some types of crystalline polymers are sometimes referred to as semi-crystalline polymers. The term "crystalline" as used herein refers to both crystalline and semi-crystalline polymers. In some embodiments, a crystalline thermoplastic polymer can have a percent crystallinity of at least 20%, for example 20 to 80%, preferably, at least 25%, for example 25 to 60%, or 25 to 30%, more preferably at least 27%, for example 27 to 40%. The term "percent crystallinity" or "% crystallinity" as used herein, refers to the portion of the polymer that has a crystalline form. The percentage is based upon the total weight of the crystalline polymer. In some embodiments, the thermoplastic polymer is amorphous. In some embodiments, an amorphous thermoplastic polymer has a crystallinity of less than 20% or less than 15%, or less than 10% crystallinity, or less than 1% crystallinity, or 0% crystallinity. In some embodiments, the thermoplastic polymer can be an amorphous polymer that does not exhibit a melting point.

[0024] The thermoplastic polymer comprises a polycarbonate, a polyetherimide, a polyimide, a polysulfone, a polyethersulfone, a polyphenylene sulfone, a polyarylene ether, a polyetherether ketone, a polyamide or a combination comprising at least one of the foregoing. In some embodiments, the thermoplastic polymer comprises polyetherimide, polycarbonate, or a combination comprising at least one of the foregoing.

[0025] In some embodiments, the thermoplastic polymer comprises a polyetherimide. Polyetherimides comprise more than 1, for example 10 to 1000, or 10 to 500, structural units of formula (1)

wherein each R is independently the same or different, and is a substituted or unsubstituted divalent organic group, such as a substituted or unsubstituted C6-20 aromatic hydrocarbon group, a substituted or unsubstituted straight or branched chain C2-20 alkylene group, a substituted or unsubstituted C3-8 cycloalkylene group, or a halogenated derivative of any of the foregoing. In some embodiments, R is a divalent group of one or more of the following formulae (2)

wherein Q1 is -O-, -S-, -C(O)-, -SO2-, -SO-, -P(Ra)(=O)- wherein Ra is a C1-8 alkyl or C6-12 aryl, -CyH2y- wherein y is an integer from 1 to 5 or a halogenated derivative thereof (which includes perfluoroalkylene groups), or -(C6H10)z- wherein z is an integer from 1 to 4. In some embodiments R is m-phenylene, p-phenylene, or a diarylene sulfone, in particular bis(4,4'-phenylene)sulfone, , bis(3,4'-phenylene)sulfone, bis(3,3'-phenylene)sulfone, or a combination comprising at least one of the foregoing. In some embodiments, at least 10 mole percent or at least 50 mole percent of the R groups contain sulfone groups, and in other embodiments no R groups contain sulfone groups.

[0026] Further in formula (1), T is -O- or a group of the formula -O-Z-O- wherein the divalent bonds of the -O-Z-O- group are in the 3,3', 3,4', 4,3', or the 4,4' positions, and Z is an aromatic C6-24 monocyclic or polycyclic moiety optionally substituted with 1 to 6 C1-8 alkyl groups, 1 to 8 halogen atoms, or a combination comprising at least one of the foregoing, provided that the valence of Z is not exceeded. Exemplary groups Z include groups of formula (3)

wherein Ra and Rb are each independently the same or different, and are a halogen atom or a monovalent C1-6 alkyl group, for example; p and q are each independently integers of 0 to 4; c is 0 to 4; and Xa is a bridging group connecting the hydroxy-substituted aromatic groups, where the bridging group and the hydroxy substituent of each C6 arylene group are disposed ortho, meta, or para (specifically para) to each other on the C6 arylene group. The bridging group Xa can be a single bond, -O-, -S-, -S(O)-, -S(O)2-, -C(O)-, or a C1-18 organic bridging group. The C1-18 organic bridging group can be cyclic or acyclic, aromatic or non-aromatic, and can further comprise heteroatoms such as halogens, oxygen, nitrogen, sulfur, silicon, or phosphorous. The C1-18 organic group can be disposed such that the C6 arylene groups connected thereto are each connected to a common alkylidene carbon or to different carbons of the C1-18 organic bridging group. A specific example of a group Z is a divalent group of formula (3a)

wherein Q is -O-, -S-, -C(O)-, -SO2-, -SO-, -P(Ra)(=O)- wherein Ra is a C1-8 alkyl or C6-12 aryl, or -CyH2y- wherein y is an integer from 1 to 5 or a halogenated derivative thereof (including a perfluoroalkylene group). In a specific embodiment Z is a derived from bisphenol A, such that Q in formula (3a) is 2,2-isopropylidene.

[0027] In an embodiment in formula (1), R is m-phenylene, p-phenylene, or a combination comprising at least one of the foregoing, and T is -O-Z-O- wherein Z is a divalent group of formula (3a). Alternatively, R is m-phenylene, p-phenylene, or a combination comprising at least one of the foregoing, and T is -O-Z-O- wherein Z is a divalent group of formula (3a) and Q is 2,2-isopropylidene. Alternatively, the polyetherimide can be a copolymer optionally comprising additional structural polyetherimide units of formula (1) wherein at least 50 mole percent (mol%) of the R groups are bis(4,4'-phenylene)sulfone, bis(3,4'-phenylene)sulfone, bis(3,3'-phenylene)sulfone, or a combination comprising at least one of the foregoing and the remaining R groups are p-phenylene, m-phenylene, or a combination comprising at least one of the foregoing; and Z is 2,2-(4-phenylene)isopropylidene, i.e., a bisphenol A moiety.

[0028] In some embodiments, the polyetherimide is a copolymer that optionally comprises additional structural imide units that are not polyetherimide units, for example imide units of the formula

wherein R is as described in formula (1) and each V is the same or different, and is a substituted or unsubstituted C6-20 aromatic hydrocarbon group, for example a tetravalent linker of the formulas

wherein W is a single bond, -O-, -S-, -C(O)-, -SO2-, -SO-, -P(Ra)(=O)- wherein Ra is a C1-8 alkyl or C6-12 aryl, or -CyH2y- wherein y is an integer from 1 to 5 or a halogenated derivative thereof (which includes perfluoroalkylene groups). These additional structural imide units preferably comprise less than 20 mol% of the total number of units, and more preferably can be present in amounts of 0 to 10 mol% of the total number of units, or 0 to 5 mol% of the total number of units, or 0 to 2 mole % of the total number of units. In some embodiments, no additional imide units are present in the polyetherimide.

[0029] The polyetherimide can be prepared by any of the methods well known to those skilled in the art, including the reaction of an aromatic bis(ether anhydride) of formula (5) or a chemical equivalent thereof, with an organic diamine of formula (6)

H2N-R-NH2 (6)
wherein T and R are defined as described above. Copolymers of the polyetherimides can be manufactured using a combination of an aromatic bis(ether anhydride) of formula (5) and an additional bis(anhydride) that is not a bis(ether anhydride), for example pyromellitic dianhydride or bis(3,4-dicarboxyphenyl) sulfone dianhydride.

[0030] Illustrative examples of aromatic bis(ether anhydride)s include 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (also known as bisphenol A dianhydride or BPADA), 3,3-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl ether dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)benzophenone dianhydride; 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl ether dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl sulfide dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy)benzophenone dianhydride; 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl sulfone dianhydride; 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl-2,2-propane dianhydride; 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl ether dianhydride; 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride; 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)benzophenone dianhydride; 4,4'-(hexafluoroisopropylidene)diphthalic anhydride; and 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride. A combination of different aromatic bis(ether anhydride)s can be used.

[0031] Examples of organic diamines include 1,4-butane diamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 1,18-octadecanediamine, 3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 4-methylnonamethylenediamine, 5-methylnonamethylenediamine, 2,5-dimethylhexamethylenediamine, 2,5-dimethylheptamethylenediamine, 2, 2-dimethylpropylenediamine, N-methyl-bis (3-aminopropyl) amine, 3-methoxyhexamethylenediamine, 1,2-bis(3-aminopropoxy) ethane, bis(3-aminopropyl) sulfide, 1,4-cyclohexanediamine, bis-(4-aminocyclohexyl) methane, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, m-xylylenediamine, p-xylylenediamine, 2-methyl-4,6-diethyl-1,3-phenylene-diamine, 5-methyl-4,6-diethyl-1,3-phenylene-diamine, benzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 1,5-diaminonaphthalene, bis(4-aminophenyl) methane, bis(2-chloro-4-amino-3,5-diethylphenyl) methane, bis(4-aminophenyl) propane, 2,4-bis(p-amino-t-butyl) toluene, bis(p-amino-t-butylphenyl) ether, bis(p-methyl-o-aminophenyl) benzene, bis(p-methyl-o-aminopentyl) benzene, 1, 3-diamino-4-isopropylbenzene, bis(4-aminophenyl) sulfide, bis-(4-aminophenyl) sulfone (also known as 4,4'-diaminodiphenyl sulfone (DDS)), and bis(4-aminophenyl) ether. Any regioisomer of the foregoing compounds can be used. C1-4 alkylated or poly(C1-4)alkylated derivatives of any of the foregoing can be used, for example a polymethylated 1,6-hexanediamine. Combinations of these compounds can also be used. In some embodiments the organic diamine is m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, or a combination comprising at least one of the foregoing.

[0032] The polyetherimides can have a melt index of 0.1 to 10 grams per minute (g/min), as measured by American Society for Testing Materials (ASTM) D1238 at 340 to 370 °C, using a 6.7 kilogram (kg) weight. In some embodiments, the polyetherimide has a weight average molecular weight (Mw) of 1,000 to 150,000 grams/mole (Dalton), as measured by gel permeation chromatography, using polystyrene standards. In some embodiments the polyetherimide has an Mw of 10,000 to 80,000 Daltons. Such polyetherimides typically have an intrinsic viscosity greater than 0.2 deciliters per gram (dl/g), or, more specifically, 0.35 to 0.7 dl/g as measured in m-cresol at 25°C.

[0033] In some embodiments, the thermoplastic polymer comprises a polycarbonate. "Polycarbonate" as used herein means a polymer or copolymer having repeating structural carbonate units of formula (7)

wherein at least 60 percent of the total number of R1 groups are aromatic, or each R1 contains at least one C6-30 aromatic group. Specifically, each R1 can be derived from a dihydroxy compound such as an aromatic dihydroxy compound of formula (8) or a bisphenol of formula (9).

In formula (8), each Rh is independently a halogen atom, for example bromine, a C1-10 hydrocarbyl group such as a C1-10 alkyl, a halogen-substituted C1-10 alkyl, a C6-10 aryl, or a halogen-substituted C6-10 aryl, and n is 0 to 4.

[0034] In formula (9), Ra and Rb are each independently a halogen, C1-12 alkoxy, or C1-12 alkyl, and p and q are each independently integers of 0 to 4, such that when p or q is less than 4, the valence of each carbon of the ring is filled by hydrogen. In an embodiment, p and q is each 0, or p and q is each 1, and Ra and Rb are each a C1-3 alkyl group, specifically methyl, disposed meta to the hydroxy group on each arylene group. Xa is a bridging group connecting the two hydroxy-substituted aromatic groups, where the bridging group and the hydroxy substituent of each C6 arylene group are disposed ortho, meta, or para (specifically para) to each other on the C6 arylene group, for example, a single bond, -O-, -S-, -S(O)-, -S(O)2-, -C(O)-, or a C1-18 organic group, which can be cyclic or acyclic, aromatic or non-aromatic, and can further comprise heteroatoms such as halogens, oxygen, nitrogen, sulfur, silicon, or phosphorous. For example, Xa can be a substituted or unsubstituted C3-18 cycloalkylidene; a C1-25 alkylidene of the formula-C(Rc)(Rd) - wherein Rc and Rd are each independently hydrogen, C1-12 alkyl, C1-12 cycloalkyl, C7-12 arylalkyl, C1-12 heteroalkyl, or cyclic C7-12 heteroarylalkyl; or a group of the formula -C(=Re)-wherein Re is a divalent C1-12 hydrocarbon group.

[0035] Some illustrative examples of dihydroxy compounds that can be used are described, for example, in WO 2013/175448 A1, US 2014/0295363, and WO 2014/072923. Specific dihydroxy compounds include resorcinol, 2,2-bis(4-hydroxyphenyl) propane ("bisphenol A" or "BPA"), 3,3-bis(4-hydroxyphenyl) phthalimidine, 2-phenyl-3,3'-bis(4-hydroxyphenyl) phthalimidine (also known as N-phenyl phenolphthalein bisphenol, "PPPBP", or 3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-1-one), 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, and 1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane (isophorone bisphenol).

[0036] "Polycarbonate" as used herein also includes copolymers comprising carbonate units and ester units ("poly(ester-carbonate)s", also known as polyester-polycarbonates). Poly(ester-carbonate)s further contain, in addition to recurring carbonate chain units of formula (1), repeating ester units of formula (10)

wherein J is a divalent group derived from a dihydroxy compound (which includes a reactive derivative thereof), and can be, for example, a C2-10 alkylene, a C6-20 cycloalkylene a C6-20 arylene, or a polyoxyalkylene group in which the alkylene groups contain 2 to 6 carbon atoms, specifically, 2, 3, or 4 carbon atoms; and T is a divalent group derived from a dicarboxylic acid (which includes a reactive derivative thereof), and can be, for example, a C2-20 alkylene, a C6-20 cycloalkylene, or a C6-20 arylene. Copolyesters containing a combination of different T or J groups can be used. The polyester units can be branched or linear.

[0037] Specific dihydroxy compounds include aromatic dihydroxy compounds of formula (8) (e.g., resorcinol), bisphenols of formula (9) (e.g., bisphenol A), a C1-8 aliphatic diol such as ethane diol, n-propane diol, i-propane diol, 1,4-butane diol, 1,6-cyclohexane diol, 1,6-hydroxymethylcyclohexane, or a combination comprising at least one of the foregoing dihydroxy compounds. Aliphatic dicarboxylic acids that can be used include C6-20 aliphatic dicarboxylic acids (which includes the terminal carboxyl groups), specifically linear C8-12 aliphatic dicarboxylic acid such as decanedioic acid (sebacic acid); and alpha, omega-C12 dicarboxylic acids such as dodecanedioic acid (DDDA). Aromatic dicarboxylic acids that can be used include terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, 1,6-cyclohexane dicarboxylic acid, or a combination comprising at least one of the foregoing acids. A combination of isophthalic acid and terephthalic acid wherein the weight ratio of isophthalic acid to terephthalic acid is 91:9 to 2:98 can be used.

[0038] Specific ester units include ethylene terephthalate units, n-propylene terephthalate units, n-butylene terephthalate units, ester units derived from isophthalic acid, terephthalic acid, and resorcinol (ITR ester units), and ester units derived from sebacic acid and bisphenol A. The molar ratio of ester units to carbonate units in the poly(ester-carbonate)s can vary broadly, for example 1:99 to 99:1, specifically, 10:90 to 90:10, more specifically, 25:75 to 75:25, or from 2:98 to 15:85.

[0039] The polycarbonates can have an intrinsic viscosity, as determined in chloroform at 25°C, of 0.3 to 1.5 deciliters per gram (dl/gm), specifically 0.45 to 1.0 dl/gm. The polycarbonates can have a weight average molecular weight of 5,000 to 200,000 Daltons, specifically 15,000 to 100,000 Daltons, as measured by gel permeation chromatography (GPC), using a crosslinked styrene-divinylbenzene column and calibrated to polycarbonate references. GPC samples are prepared at a concentration of 1 mg per ml (mg/ml), and are eluted at a flow rate of 1.5 ml per minute.

[0040] In some embodiments, the powder composition can further comprise one or more optional components. An optional component is present in a sufficient amount to perform its intended function without adversely affecting the powder composition or an article prepared therefrom. For example, the one or more optional components can comprise a particulate inorganic filler (such as glass, ceramic, or metal, e.g., ceramic particles), a particulate organic filler (such as carbon or a crosslinked polymer), conductive filler (such as graphite or single-walled or multi-walled carbon nanotubes), an inorganic filler, organic fiber, inorganic fiber, conductive ink, antioxidant, heat stabilizer, light stabilizer, ultraviolet (UV) light stabilizer, UV absorbing additive, NIR absorbing additive, IR absorbing additive, laser marking dye, plasticizer, lubricant, release agent (such as a mold release agent), antistatic agent, anti-fog agent, antimicrobial agent, colorant (e.g, a dye or pigment), surface effect additive, radiation stabilizer, flame retardant, anti-drip agent (e.g., a PTFE-encapsulated styrene-acrylonitrile copolymer (TSAN)), a fragrance, or a combination comprising at least one of the foregoing. When present, each individual optional component can be included in the powder composition in an amount of 0.01 to 30 wt%, based on the total weight of the powder composition. The total amount of all optional components in the powder composition ranges from 0 up to 30 wt%, based on the total weight of the powder composition. For example, the total amount of the additive composition (other than any filler) can be 0.001 to 10.0 wt%, or 0.01 to 5 wt%, each based on the total weight of the first solution.

[0041] The powder composition can optionally contain a flow promoter. The flow promoter preferably is present in an amount sufficient to provide the particles with a flowability of greater than or equal to 4, more preferably greater than or equal to 10. In some embodiments, the powder composition can include a flow promoter in an amount of 0.005 to 1 wt%, based on the total weight of the powder composition.

[0042] The optional flow promoter, when included in the powder composition, can include an unmodified fumed metal oxide, a hydrophobic fumed metal oxide, a hydrophilic fumed metal oxide, or a combination comprising at least one of the foregoing. In some embodiments, the flow promoter can be fumed silica, fumed aluminum oxide, a hydrated silica, amorphous alumina, a glassy silica, a glassy phosphate, a glassy borate, a glassy oxide, titania, talc, mica, a fumed silica, kaolin, attapulgite, calcium silicate, alumina, magnesium silicate, or a combination comprising at least one of the foregoing, more preferably fumed silica.

[0043] Another optional component is a coloring agent, for example a pigment or a dye, like carbon black, to impart a desired color to the article of manufacture. The coloring agent is not limited, as long as the coloring agent does not adversely affect the composition or an article prepared therefrom, and is sufficiently stable to retain its color under conditions of the laser sintering process and during exposure to the laser.

[0044] The powder compositions described herein can be particularly useful for a variety of applications, including forming three dimensional articles or powder coatings. Accordingly, another aspect of the present disclosure includes a method of preparing a powder coating comprises applying a powder coating layer comprising the above-described powder composition to a substrate, and consolidating the powder coating layer to form the powder coating. Applying the powder coating layer can be by any method that is generally known, for example by scattering, sprinkling, spraying, thermal or flame spraying, electrostatic spraying, or by fluidized bed coating methods. In some embodiments, the particles or the substrate can be given an electrostatic charge so that they will adhere well. Examples of substrates that can be coated include, but are not limited to, glass, plastic, wood, metal, ceramics, or a combination comprising at least one of the foregoing substrates. These substrates can be used as part of any number of different articles. Consolidating the powder coating layer to form the powder coating can include applying heat or pressure or both to coalesce or fuse the particles to form the powder coating. Heating can be achieved at a temperature above the melting range of the powder composition, for example in a temperature range of 80 to 220°C. The temperature is dependent on the type of thermoplastic particles. The heating can be by gas or air heating, or IR or NIR, as known in the art. A powder-coated article made by the above method represents another aspect of the present disclosure.

[0045] In another embodiment, the present disclosure includes a method of preparing a three-dimensional article comprising compression molding the powder composition to form the three-dimensional object.

[0046] In yet another embodiment, the powder compositions of the present disclosure can be fusible powder compositions, and therefore can be particularly useful in a powder bed fusing process. The term "powder bed fusing" or "powder bed fusion" as used herein refers to processes wherein the powder is selectively sintered or melted and fused, layer-by-layer to provide a three-dimensional article. Sintering can result in articles having a density of less than about 90% of the density of the solid powder composition, whereas melting can provide objects having a density of 90%-100% of the solid powder composition. Powder bed fusing or powder bed fusion further includes all laser sintering and all selective laser sintering processes as well as other powder bed fusing technologies as defined by ASTM F2792-12a. For example, sintering of the powder composition can be accomplished via application of electromagnetic radiation other than that produced by a laser, with the selectivity of the sintering achieved, for example, through selective application of inhibitors, absorbers, susceptors, or the electromagnetic radiation (e.g., through use of masks or directed laser beams). Any other suitable source of electromagnetic radiation can be used, including, for example, infrared radiation sources, microwave generators, lasers, radiative heaters, lamps, or a combination thereof. In some embodiments, selective mask sintering ("SMS") techniques can be used to produce three-dimensional articles of the invention. For further discussion of SMS processes, see for example U.S. Pat. No. 6,531,086 which describes an SMS machine in which a shielding mask is used to selectively block infrared radiation, resulting in the selective irradiation of a portion of a powder layer. If using an SMS process to produce articles from powder compositions of the invention, it can be desirable to include one or more materials in the powder composition that enhance the infrared absorption properties of the powder composition. For example, the powder composition can include one or more heat absorbers or dark-colored materials (e.g., carbon black, carbon nanotubes, or carbon fibers).

[0047] Powder bed fused (e.g., laser sintered) articles can include a plurality of overlying and adherent sintered layers that include a polymeric matrix which, in some embodiments, have reinforcement particles dispersed throughout the polymeric matrix. "Plurality" as used in the context of additive manufacturing includes 5 or more layers, or 20 or more layers. The maximum number of layers can vary greatly, determined, for example, by considerations such as the size of the article being manufactured, the technique used, the capabilities of the equipment used, and the level of detail desired in the final article. For example, 5 to 100,000 layers can be formed, or 20 to 50,000 layers can be formed, or 50 to 50,000 layers can be formed. As used herein, "layer" is a term of convenience that includes any shape, regular or irregular, having at least a predetermined thickness. In some embodiments, the size and configuration two dimensions are predetermined, and in some embodiments, the size and shape of all three-dimensions of the layer is predetermined. The thickness of each layer can vary widely depending on the additive manufacturing method. In some embodiments the thickness of each layer as formed differs from a previous or subsequent layer. In some embodiments, the thickness of each layer is the same. In some embodiments the thickness of each layer as formed is 0.5 millimeters (mm) to 5 mm. In some embodiments, the fused layers of powder bed fused articles can be of any thickness suitable for selective laser sintered processing. For example, the individual layers can be each, on average, preferably at least 50 micrometers (µm) thick, more preferably at least 80 µm thick, and even more preferably at least 100 µm thick. In a preferred embodiment, the plurality of sintered layers are each, on average, preferably less than 500 µm thick, more preferably less than 300 µm thick, and even more preferably less than 200 µm thick. Thus, the individual layers for some embodiments can be 50 to 500 µm, 80 to 300 µm, or 100 to 200 µm thick. Three-dimensional articles produced from powder compositions of the invention using a layer-by-layer powder bed fusing processes other than selective laser sintering can have layer thicknesses that are the same or different from those described above.

[0048] Laser sintering processes are sufficiently well known, and are based on the selective sintering of polymer particles, where layers of polymer particles are briefly exposed to laser light and the polymer particles exposed to the laser light are thus bonded to one another. Successive sintering of layers of polymer particles produces three-dimensional objects. Details concerning the selective laser sintering process are found, by way of example, in U.S. Pat. No. 6,136,948 and WO 96/06881.

[0049] An example of a SLS system for fabricating a three-dimensional article from the powder composition can be described as follows. One thin layer of powder composition comprising the powder composition is spread over the sintering chamber. The laser beam traces the computer-controlled pattern, corresponding to the cross-section slice of the CAD model, to melt the powder selectively which has been preheated to slightly, preferably below its melting temperature. After one layer of powder is sintered, the powder bed piston is lowered with a predetermined increment (typically 100 µm), and another layer of powder is spread over the previous sintered layer by a roller. The process then repeats as the laser melts and fuses each successive layer to the previous layer until the entire article is completed.

[0050] In some embodiments, a typical sintering process, such as described above, can use a powder comprising thermoplastic particles that exhibit a melting transition (e.g., a melting temperature, Tm), which aids in obtaining a distinct region that is intended to be fused. The heat generated can diffuse away from the region of interest, however the temperature can decrease to below the melting temperature of the particles rapidly. Accordingly, outside the region of interest the powder composition advantageously remains in the unfused form. In contrast, in embodiments utilizing particles that do not exhibit a melting point (e.g., amorphous polymers), particle fusion is possible everywhere the temperature is above the glass transition temperature (Tg). In order to obtain a similar level of resolution in a three-dimensional article prepared by powder bed fusing amorphous polymer particles, the present inventors have determined that the timing of the coalescence during a powder bed fusion process is dependent on particle size. The time scale of the coalescence process can be estimated as the time for the volume V of polymer in the particle to flow through an opening the size of the particle. The velocity, U, is proportional to the driving pressure divided by the viscosity µ, as shown in the following relationship.

The time scale, τ, is given by the relationship

wherein y is the surface tension of the molten particle, R is the particle radius, and A = π R2.

[0051] The quadratic dependence of the coalescence time scale on particle size is evident from the relationship above. Shorter time scales can lead to shorter heating cycles, and thus better resolution in the final article. Thus, by careful selection of the particle size of the powder compositions, the present disclosure can advantageously provide powder compositions comprising amorphous thermoplastic polymers for additive manufacturing processes (e.g., selective laser sintering). Accordingly, in some embodiments, preferably in embodiments where thermoplastic particles comprising an amorphous polymer are used, the powder composition preferably comprises thermoplastic particles having a first D50 of 100 nm to 50 µm, preferably 150 nm to 25 µm, more preferably 200 nm to 10 µm.

[0052] Another aspect of the present disclosure includes three-dimensional articles made by powder bed fusing the powder compositions. After a layer-by-layer manufacture of an article of manufacture, the article can exhibit excellent resolution, durability, and strength. These articles of manufacture can have a wide variety of uses, including as prototypes and as end products as well as molds for end products.

[0053] The compositions, methods, and articles described herein are further illustrated by the following non-limiting example.

EXAMPLES



[0054] FIG. 3 shows a particle size distribution of a powder used for the following examples. The powder comprises a polyetherimide obtained as ULTEM 1000 from SABIC. The particle size distribution was obtained using a diffractometer. As can be seen from FIG. 3, the distribution of sizes is broad, ranging from 1 to 100 micrometers.

[0055] To demonstrate the improved sintering performance of a powder having an optimized particle size distribution, the powder sample was fractionated according to size by sedimentation. The fractions were recombined at 89% of the particle size distribution having a volume averaged size of Dv, and 11% of the particle size distribution having a peak size equal to 0.414 times Dv. The particle size distributions of the two components, and the particle size distribution resulting from their combination, are shown in FIG. 4.

[0056] A marked improvement in the flowability of the combined particle size distribution was noted. The bulk powder exhibited a flowability (ffc) of 1 to 5. The "optimized" powder having the combined particle size distribution was both displaced vertically and had a greater range of improvement with the presence of flow promoting nanoparticles. For example, FIG. 5 shows the flowability as a function of flow promoter content (in terms of relative surface area coverage (SAC)) for the bulk powder and the optimized powder. The flow promoter was an aluminum oxide flow promoter (obtained as AEROXIDE AluC from Evonik Industries). Notably, the optimized powder was observed to reasonably flow even without the presence of a flow modifier, whereas the bulk powder exhibited substantially cohesive behavior.

[0057] The bulk and optimized powder samples were then tested for their utility in SLS. Impact bars (40 x 10 x 2 millimeters) were printed on a SLS printer. During the SLS printing, the optimized powder was observed to exhibit good flowability, even at high temperature, and filling of the fresh powder on sintered areas was homogenous. In contrast, the flowability of the bulk powder was uneven and was observed to worsen at elevated temperatures, resulting in voids in the printed parts. Furthermore, the melt behavior of the optimized powder was observed to be improved relative to the bulk powder (i.e., burned areas were not observed even at high laser power with the optimized powder, whereas the bulk powder exhibited burning at similar laser powers).

[0058] Additionally, in typical printing processes, for example using bulk materials, a significant amount of powder sticks to the printed parts, even after cleaning by sand blasting. In contrast, almost no excess powder remained on the printed parts printed from the optimized powder sample after treatment by sandblasting.

[0059] The density of the printed impact bars was measured. The impact bars prepared from the bulk powder exhibited densities of 0.9506 to 0.9729 grams per milliliter. The impact bars prepared from the optimized powder exhibited densities of 1.2378 to 1.2432 grams per milliliter. The commercial polyetherimide itself from which the powders were prepared has a density of 1.27 grams per milliliter. So the bars printed from the optimized powders had a density of about 97.7% that of the commercial polyetherimide sample, whereas bars from the bulk powder exhibited a density of 75.8% that of the commercial polyetherimide sample.

[0060] As used herein, the term "hydrocarbyl" includes groups containing carbon, hydrogen, and optionally one or more heteroatoms (e.g., 1, 2, 3, or 4 atoms such as halogen, O, N, S, P, or Si). "Alkyl" means a branched or straight chain, saturated, monovalent hydrocarbon group, e.g., methyl, ethyl, i-propyl, and n-butyl. "Alkylene" means a straight or branched chain, saturated, divalent hydrocarbon group (e.g., methylene (-CH2-) or propylene (-(CH2)3-)). "Alkenyl" and "alkenylene" mean a monovalent or divalent, respectively, straight or branched chain hydrocarbon group having at least one carbon-carbon double bond (e.g., ethenyl (-HC=CH2) or propenylene (-HC(CH3)=CH2-). "Alkynyl" means a straight or branched chain, monovalent hydrocarbon group having at least one carbon-carbon triple bond (e.g., ethynyl). "Alkoxy" means an alkyl group linked via an oxygen (i.e., alkyl-O-), for example methoxy, ethoxy, and sec-butyloxy. "Cycloalkyl" and "cycloalkylene" mean a monovalent and divalent cyclic hydrocarbon group, respectively, of the formula -CnH2n-x and -CnH2n-2x- wherein x is the number of cyclization(s). "Aryl" means a monovalent, monocyclic or polycyclic aromatic group (e.g., phenyl or naphthyl). "Arylene" means a divalent, monocyclic or polycyclic aromatic group (e.g., phenylene or naphthylene). The prefix "halo" means a group or compound including one more halogen (F, Cl, Br, or I) substituents, which can be the same or different. The prefix "hetero" means a group or compound that includes at least one ring member that is a heteroatom (e.g., 1, 2, or 3 heteroatoms, wherein each heteroatom is independently N, O, S, or P.

[0061] "Substituted" means that the compound or group is substituted with at least one (e.g., 1, 2, 3, or 4) substituents instead of hydrogen, where each substituent is independently nitro (-NO2), cyano (-CN), hydroxy (-OH), halogen, thiol (-SH), thiocyano (-SCN), C1-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, C1-6 haloalkyl, C1-9 alkoxy, C1-6 haloalkoxy, C3-12 cycloalkyl, C5-18 cycloalkenyl, C6-12 aryl, C7-13 arylalkylene (e.g, benzyl), C7-12 alkylarylene (e.g, toluyl), C4-12 heterocycloalkyl, C3-12 heteroaryl, C1-6 alkyl sulfonyl (-S(=O)2-alkyl), C6-12 arylsulfonyl (-S(=O)2-aryl), or tosyl (CH3C6H4SO2-), provided that the substituted atom's normal valence is not exceeded, and that the substitution does not significantly adversely affect the manufacture, stability, or desired property of the compound. When a compound is substituted, the indicated number of carbon atoms is the total number of carbon atoms in the group, including those of the substituent(s).


Claims

1. A powder composition, comprising:
a plurality of thermoplastic particles characterized by a bimodal particle size distribution comprising, based on the total weight of the particles,

85 to 94, preferably 87 to 91, more preferably 89 weight percent of the particles having a first D50 as determined by laser diffraction of 1 nm to 500 micrometers; and

6 to 15, preferably 9 to 13, more preferably 11 weight percent of the particles having a D50 that is 0.414 times the first D50;

wherein the thermoplastic polymer is a polycarbonate, a polyetherimide, a polyimide, a polysulfone, a polyethersulfone, a polyphenylene sulfone, a polyarylene ether, a polyetherether ketone, a polyamide or a combination comprising at least one of the foregoing.


 
2. A powder composition, comprising:
a plurality of thermoplastic particles characterized by a bimodal particle size distribution comprising, based on the total weight of the particles,

67 to 77, preferably 70 to 74, more preferably 72 weight percent of the particles having a first D50 as determined by laser diffraction of 1 nm to 500 micrometers; and

23 to 33, preferably 26 to 30, more preferably 28 weight percent of the particles having a second D50 that is 0.732 times the first D50;

wherein the thermoplastic polymer is a polycarbonate, a polyetherimide, a polyimide, a polysulfone, a polyethersulfone, a polyphenylene sulfone, a polyarylene ether, a polyetherether ketone, a polyamide or a combination comprising at least one of the foregoing.


 
3. A powder composition, comprising:
a plurality of thermoplastic particles characterized by a trimodal particle size distribution comprising, based on the total weight of the particles,

66 to 76, preferably 69 to 73, more preferably 71 weight percent of the particles having a first D50 as determined by laser diffraction of 1 nm to 500 micrometers;

23 to 33, preferably 26 to 30, more preferably 28 weight percent of the particles having a second D50 that is 0.732 times the first D50; and

0.5 to 5, preferably 1 to 3, more preferably 1 weight percent of the particles having a third D50 that is 0.268 times the first D50;

wherein the thermoplastic polymer is a polycarbonate, a polyetherimide, a polyimide, a polysulfone, a polyethersulfone, a polyphenylene sulfone, a polyarylene ether, a polyetherether ketone, a polyamide or a combination comprising at least one of the foregoing.


 
4. The powder composition of any one or more of claims 1 to 3, wherein the first D50 is from 15 nm to 100 µm, more preferably from 25 nm to 50 µm.
 
5. The powder composition of any one or more of claims 1 to 3, wherein the first D50 is from 100 nm to 50 µm, preferably from 150 nm to 25 µm, more preferably from 200 nm to 10 µm.
 
6. The powder composition of any one or more of claims 1 to 5, wherein the thermoplastic polymer is a polycarbonate, a polyetherimide, or a combination comprising at least one of the foregoing.
 
7. The powder composition of any one or more of claims 1 to 6, wherein the thermoplastic polymer is amorphous.
 
8. The powder composition of any one or more of claims 1 to 7, further comprising a flow promoter in an amount of 0.005 to 1 weight percent, based on the weight of the thermoplastic polymer particles, to provide particles having a flowability of greater than or equal to 4, more preferably greater than or equal to 10.
 
9. The powder composition of claim 8, wherein the flow promoter comprises an unmodified fumed metal oxide, a hydrophobic fumed metal oxide, a hydrophilic fumed metal oxide, or a combination comprising at least one of the foregoing, preferably fumed silica, fumed aluminum oxide, a hydrated silica, amorphous alumina, a glassy silica, a glassy phosphate, a glassy borate, a glassy oxide, titania, talc, mica, a fumed silica, kaolin, attapulgite, calcium silicate, alumina, magnesium silicate, or a combination comprising at least one of the foregoing, more preferably fumed silica.
 
10. The powder composition of any one or more of claims 1 to 9, wherein the thermoplastic particles have a sphericity of 0.9 to 1, or wherein the thermoplastic particles each have a minimum and a maximum radius of within 10%, preferably within 5%.
 
11. A method of preparing a three-dimensional article, the method comprising:
powder bed fusing the powder composition of any one or more of claims 1 to 10 to form a three-dimensional article, wherein the powder bed fusing comprises selective laser sintering.
 
12. A three-dimensional article made by the method of claim 11.
 
13. A method of preparing a powder coating, the method comprising:

applying a powder coating layer comprising the powder composition of any one or more of claims 1 to 10 to a substrate; and

consolidating the powder coating layer to form the powder coating.


 
14. A powder-coated article made by the method of claim 13.
 
15. A method of preparing a three-dimensional article, the method comprising:
compression molding the powder composition of any one or more of claims 1 to 10 to form the three-dimensional article.
 


Ansprüche

1. Pulverzusammensetzung, umfassend:
eine Mehrzahl thermoplastischer Partikel, die durch eine bimodale Partikelgrößenverteilung gekennzeichnet ist, welche bezogen auf das Gesamtgewicht der Partikel Folgendes umfasst

85 bis 94, vorzugsweise 87 bis 91, insbesondere 89 Gewichtsprozent an Partikeln mit einem ersten D50-Wert, der gemäß einer Bestimmung mittels Laserbeugung 1 nm bis 500 Mikrometer beträgt; und

6 bis 15, vorzugsweise 9 bis 13, insbesondere 11 Gewichtsprozent an Partikeln mit einem D50-Wert, welcher dem 0,414-fachen des ersten D50-Werts entspricht;

wobei es sich bei dem thermoplastischen Polymer um ein Polycarbonat, ein Polyetherimid, ein Polyimid, ein Polysulfon, ein Polyethersulfon, ein Polyphenylensulfon, einen Polyarylenether, ein Polyetheretherketon, ein Polyamid oder um eine Kombination handelt, die mindestens eines der vorstehend genannten umfasst.


 
2. Pulverzusammensetzung, umfassend:
eine Mehrzahl thermoplastischer Partikel, die durch eine bimodale Partikelgrößenverteilung gekennzeichnet ist, welche bezogen auf das Gesamtgewicht der Partikel Folgendes umfasst

67 bis 77, vorzugsweise 70 bis 74, insbesondere 72 Gewichtsprozent an Partikeln mit einem ersten D50-Wert, der gemäß einer Bestimmung mittels Laserbeugung 1 nm bis 500 Mikrometer beträgt; und

23 bis 33, vorzugsweise 26 bis 30, insbesondere 28 Gewichtsprozent an Partikeln mit einem zweiten D50-Wert, welcher dem 0,732-fachen des ersten D50-Werts entspricht;

wobei es sich bei dem thermoplastischen Polymer um ein Polycarbonat, ein Polyetherimid, ein Polyimid, ein Polysulfon, ein Polyethersulfon, ein Polyphenylensulfon, einen Polyarylenether, ein Polyetheretherketon, ein Polyamid oder um eine Kombination handelt, die mindestens eines der vorstehend genannten umfasst.


 
3. Pulverzusammensetzung, umfassend:
eine Mehrzahl thermoplastischer Partikel, die durch eine trimodale Partikelgrößenverteilung gekennzeichnet ist, welche bezogen auf das Gesamtgewicht der Partikel Folgendes umfasst

66 bis 76, vorzugsweise 69 bis 73, insbesondere 71 Gewichtsprozent an Partikeln mit einem ersten D50-Wert, der gemäß einer Bestimmung mittels Laserbeugung 1 nm bis 500 Mikrometer beträgt;

23 bis 33, vorzugsweise 26 bis 30, insbesondere 28 Gewichtsprozent an Partikeln mit einem zweiten D50-Wert, welcher dem 0,732-fachen des ersten D50-Werts entspricht; und

0,5 bis 5, vorzugsweise 1 bis 3, insbesondere 1 Gewichtsprozent an Partikeln mit einem dritten D50-Wert, welcher dem 0,268-fachen des ersten D50-Werts entspricht;

wobei es sich bei dem thermoplastischen Polymer um ein Polycarbonat, ein Polyetherimid, ein Polyimid, ein Polysulfon, ein Polyethersulfon, ein Polyphenylensuldon, einen Polyarylenether, ein Polyetheretherketon, ein Polyamid oder um eine Kombination handelt, die mindestens eines der vorstehend genannten umfasst.


 
4. Pulverzusammensetzung nach einem oder mehreren der Ansprüche 1 bis 3, wobei der erste D50-Wert im Bereich von 15 nm bis 100 µm, insbesondere von 25 nm bis 50 µm, liegt.
 
5. Pulverzusammensetzung nach einem oder mehreren der Ansprüche 1 bis 3, wobei der erste D50-Wert im Bereich von 100 nm bis 50 µm, vorzugsweise von 150 nm bis 25 µm, insbesondere von 200 nm bis 10 µm, liegt.
 
6. Pulverzusammensetzung nach einem beliebigen der Ansprüche 1 bis 5, wobei es sich bei dem thermoplastischen Polymer um ein Polycarbonat, ein Polyetherimid oder um eine Kombination handelt, die mindestens eines der vorstehend genannten umfasst.
 
7. Pulverzusammensetzung nach einem oder mehreren der Ansprüche 1 bis 6, wobei das thermoplastische Polymer amorph ist.
 
8. Pulverzusammensetzung nach einem oder mehreren der Ansprüche 1 bis 7, die weiterhin ein Fließhilfsmittel in einer Menge von 0,005 bis 1 Gewichtsprozent umfasst, bezogen auf das Gewicht der thermoplastischen Polymerpartikel, um Partikel bereitzustellen, die eine Fließfähigkeit von mindestens 4, insbesondere von mindestens 10, aufweisen.
 
9. Pulverzusammensetzung nach Anspruch 8, wobei das Fließhilfsmittel ein unmodifiziertes pyrogenes Metalloxid, ein hydrophobes pyrogenes Metalloxid, ein hydrophiles pyrogenes Metalloxid oder eine Kombination umfasst, die mindestens eines der vorstehend genannten umfasst, wobei es sich vorzugsweise um pyrogene Kieselsäure, pyrogenes Aluminiumoxid, eine als Hydrat vorliegende Kieselsäure, amorphes Aluminiumoxid, eine glasartige Kieselsäure, ein glasartiges Phosphat, ein glasartiges Borat, ein glasartiges Oxid, Titandioxid, Talkum, Glimmer, eine pyrogene Kieselsäure, Kaolin, Attapulgit, Calciumsilicat, Aluminiumoxid, Magnesiumsilikat oder um eine Kombination handelt, die mindestens eines der vorstehend genannten umfasst, insbesondere um pyrogene Kieselsäure.
 
10. Pulverzusammensetzung nach einem beliebigen der Ansprüche 1 bis 9, wobei die thermoplastischen Partikel eine Sphärizität von 0,9 bis 1 haben oder wobei die Minimal- und Maximalradien der thermoplastischen Partikel sich jeweils um höchstens 10 % unterscheiden, vorzugsweise um höchstens 5 %.
 
11. Verfahren zum Herstellen eines dreidimensionalen Gegenstands, wobei das Verfahren Folgendes umfasst: pulverbettbasiertes Schmelzen der Pulverzusammensetzung nach einem oder mehreren beliebigen der Ansprüche 1 bis 10, um einen dreidimensionalen Gegenstand herzustellen, wobei das pulverbettbasierte Schmelzen ein selektives Lasersintern umfasst.
 
12. Dreidimensionaler Gegenstand, der mittels des Verfahrens nach Anspruch 11 hergestellt ist.
 
13. Verfahren zum Herstellen einer Pulverbeschichtung, wobei das Verfahren Folgendes umfasst:

Aufbringen einer Pulverbeschichtungslage, welche die Pulverzusammensetzung nach einem oder mehreren beliebigen der Ansprüche 1 bis 10 umfasst; und

Verfestigen der Pulverbeschichtungslage, um die Pulverbeschichtung zu bilden.


 
14. Pulverbeschichteter Gegenstand, der mittels des Verfahrens nach Anspruch 13 hergestellt ist.
 
15. Verfahren zum Herstellen eines dreidimensionalen Gegenstands, wobei das Verfahren Folgendes umfasst:
Presssintern der Pulverzusammensetzung nach einem oder mehreren beliebigen der Ansprüche 1 bis 10, um den dreidimensionalen Gegenstand herzustellen.
 


Revendications

1. Composition en poudre, comprenant :

une pluralité de particules thermoplastiques caractérisée par une distribution granulométrique bimodale comprenant, par rapport au poids total des particules,

85 à 94, de préférence 87 à 91, plus préférablement, 89 pour cent en poids des particules ayant un premier D50 tel que déterminé par diffraction laser de 1 nm à 500 micromètres ; et

6 à 15, de préférence 9 à 13, plus préférablement 11 pour cent en poids des particules ayant un D50 qui est 0,414 fois le premier D50 ;

dans laquelle le polymère thermoplastique est un polycarbonate, un polyétherimide, un polyimide, une polysulfone, une polyéthersulfone, une polyphénylène sulfone, un polyarylène éther, une polyétheréther cétone, un polyamide ou une combinaison comprenant au moins l'un des polymères précédents.


 
2. Composition en poudre, comprenant :

une pluralité de particules thermoplastiques caractérisée par une distribution granulométrique bimodale comprenant, par rapport au poids total des particules,

67 à 77, de préférence 70 à 74, plus préférablement 72 pour cent en poids des particules ayant un premier D50 tel que déterminé par diffraction laser de 1 nm à 500 micromètres ; et

23 à 33, de préférence 26 à 30, plus préférablement 28 pour cent en poids des particules ayant un deuxième D50 qui est 0,732 fois le premier D50 ;

dans laquelle le polymère thermoplastique est un polycarbonate, un polyétherimide, un polyimide, une polysulfone, une polyéthersulfone, une polyphénylène sulfone, un polyarylène éther, une polyétheréther cétone, un polyamide ou une combinaison comprenant au moins l'un des polymères précédents.


 
3. Composition en poudre, comprenant :

une pluralité de particules thermoplastiques caractérisée par une distribution granulométrique trimodale comprenant, par rapport au poids total des particules,

66 à 76, de préférence 69 à 73, plus préférablement 71 pour cent en poids des particules ayant un premier D50 tel que déterminé par diffraction laser de 1 nm à 500 micromètres ;

23 à 33, de préférence 26 à 30, plus préférablement 28 pour cent en poids des particules ayant un deuxième D50 qui est 0,732 fois le premier D50 ; et

0,5 à 5, de préférence 1 à 3, plus préférablement 1 pour cent en poids des particules ayant un troisième D50 qui est 0,268 fois le premier D50 ;

dans laquelle le polymère thermoplastique est un polycarbonate, un polyétherimide, un polyimide, une polysulfone, une polyéthersulfone, une polyphénylène sulfone, un polyarylène éther, une polyétheréther cétone, un polyamide ou une combinaison comprenant au moins l'un des polymères précédents.


 
4. Composition en poudre selon l'une quelconque ou plusieurs des revendications 1 à 3, dans laquelle le premier D50 est de 15 nm à 100 µm, plus préférablement de 25 nm à 50 µm.
 
5. Composition en poudre selon l'une quelconque ou plusieurs des revendications 1 à 3, dans laquelle le premier D50 est de 100 nm à 50 µm, de préférence de 150 nm à 25 µm, plus préférablement de 200 nm à 10 µm.
 
6. Composition en poudre selon l'une quelconque ou plusieurs des revendications 1 à 5, dans laquelle le polymère thermoplastique est un polycarbonate, un polyétherimide, ou une combinaison comprenant au moins l'un des polymères précédents.
 
7. Composition en poudre selon l'une quelconque ou plusieurs des revendications 1 à 6, dans laquelle le polymère thermoplastique est amorphe.
 
8. Composition en poudre selon l'une quelconque ou plusieurs des revendications 1 à 7, comprenant en outre un agent favorisant l'écoulement en une quantité de 0,005 à 1 pour cent en poids, par rapport au poids des particules de polymère thermoplastique, pour fournir des particules présentant une aptitude à l'écoulement supérieure ou égale à 4, plus préférablement supérieure ou égale à 10.
 
9. Composition en poudre selon la revendication 8, dans laquelle l'agent favorisant l'écoulement comprend un oxyde de métal fumé non modifié, un oxyde de métal fumé hydrophobe, un oxyde de métal fumé hydrophile, ou une combinaison comprenant au moins l'un des agents précédents, de préférence de la silice fumée, de l'oxyde d'aluminium fumé, une silice hydratée, de l'alumine amorphe, une silice vitreuse, un phosphate vitreux, un borate vitreux, un oxyde vitreux, de l'oxyde de titane, du talc, du mica, une silice fumée, du kaolin, de l'attapulgite, du silicate de calcium, de l'alumine, du silicate de magnésium, ou une combinaison comprenant au moins l'un des agents précédents, plus préférablement de la silice fumée.
 
10. Composition en poudre selon l'une quelconque ou plusieurs des revendications 1 à 9, dans laquelle les particules thermoplastiques ont une sphéricité de 0,9 à 1, ou dans laquelle les particules thermoplastiques ont chacune un rayon minimum et un rayon maximum dans une limite de 10 %, de préférence dans une limite de 5 %.
 
11. Procédé de préparation d'un article tridimensionnel, le procédé comprenant :
la fusion d'un lit de poudre de la composition en poudre selon l'une quelconque ou plusieurs des revendications 1 à 10 pour former un article tridimensionnel, dans lequel la fusion de lit de poudre comprend un frittage laser sélectif.
 
12. Article tridimensionnel fabriqué selon le procédé de la revendication 11.
 
13. Procédé de préparation d'un revêtement en poudre, le procédé comprenant :

l'application d'une couche de revêtement en poudre comprenant la composition en poudre selon l'une quelconque ou plusieurs des revendications 1 à 10 à un substrat ; et

la consolidation de la couche de revêtement en poudre pour former le revêtement en poudre.


 
14. Article revêtu de poudre fabriqué selon le procédé de la revendication 13.
 
15. Procédé de préparation d'un article tridimensionnel, le procédé comprenant :
le moulage par compression de la composition en poudre selon l'une quelconque ou plusieurs des revendications 1 à 10 pour former l'article tridimensionnel.
 




Drawing











Cited references

REFERENCES CITED IN THE DESCRIPTION



This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description