Powder compositions and methods of manufacturing articles therefrom

Patent metadata

Field	Value
Publication number	US-9611355-B2
Application number	US-92164609-A
Country	US
Kind code	B2
Filing date	Mar 12, 2009
Priority date	Mar 14, 2008
Publication date	Apr 4, 2017
Grant date	Apr 4, 2017

Abstract

Powder compositions and articles and methods of forming articles from powder compositions are provided. The powder compositions include at least one powder that preferably includes an amount of one or more branched polymers such as, for example, one or more branched polyamide polymers. The powder composition is preferably capable of being formed, via a layer-by-layer sintering process such as, for example, selective laser sintering, into a three-dimensional article.

First claim

What is claimed is:

1. A powder composition, comprising:
a laser-sinterable powder including at least 20 weight percent of a polyamide polymer component;
wherein the polyamide polymer component includes one or more branched polyamide polymers in an amount that comprises at least 5 weight percent of the laser-sinterable powder, wherein the branched polyamide comprises a star polymer having a single branching unit and at least 3 oligomer or polymer arms covalently attached to the branching unit, wherein the single branching unit is formed from a polycarboxylic acid, wherein at least one of the oligomer or polymer arms comprises a reaction product of reactants including a C11-C20 amino acid, a C11-C20 lactam, or a mixture thereof, and wherein the powder composition has a melt enthalpy of less than 100 J/g and a sintering window of less than 40° C.

2. The powder composition of claim 1 , wherein the oligomer or polymer arms are attached to the branching unit via amide linkages.

3. The powder composition of claim 1 , wherein the polycarboxylic acid is chosen from benzene-pentacarboxylic acid; mellitic acid; 1,3,5,7-naphthalene-tetracarboxylic acid; 2,4,6-pyridine-tricarboxylic acid; pyromellitic acid; trimellitic acid; trimesic acid; 3,5,3′,5′-biphenyltetracarboxylic acid; 3,5,3′,5′-bipyridyltetracarboxylic acid; 3,5,3′,5′-benzophenonetetracarboxylic acid; 1,3,6,8-acridinetetracarboxylic acid; 1,2,4,5-benzenetetracarboxylic acid; and anhydrides, amides, or esters thereof; or a mixture thereof.

4. The powder composition of claim 1 , wherein the polycarboxylic acid comprises trimesic acid.

5. The powder composition of claim 1 , wherein at least one of the oligomer or polymer arms comprises a reaction product of reactants including a C2-C20 amino acid, a C4-C20 lactam, or a mixture thereof.

6. The powder composition of claim 1 , wherein the branched polyamide includes a nylon-11 branch unit, a nylon-12 branch unit, or a combination thereof.

7. The powder composition of claim 1 , wherein the branched polyamide includes polyamide branch units formed from laurolactam, aminoundecanoic acid, or a mixture thereof.

8. The powder composition of claim 1 , wherein the polyamide polymer component includes at least 3 carboxylic end groups per amine end group.

9. The powder composition of claim 1 , wherein the laser-sinterable powder comprises a ground powder.

10. The powder composition of claim 9 , wherein a test specimen exhibits an elongation at break of at least 3% when the powder composition is laser-sintered to form the test specimen.

11. The powder composition of claim 1 , wherein the branched polyamide is a reaction product of one or more AB compound and one or more B n compound, wherein:
A and B are functional groups capable of reacting with one another;
n denotes the number of B functional groups present in the B n compound, and wherein n is 3 or more;
B is a carboxylic group; the AB compound is a cyclic amide, an amino acid, or a combination thereof and
the stoichiometry of the mole equivalents of Bn compound to mole equivalents of AB compound ranges from 0.0001:1 to 0.03:1.

12. The powder composition of claim 1 , wherein the powder composition has a melt enthalpy of 60 J/g to 70 J/g.

13. The powder composition of claim 1 , wherein the branched polyamide includes a nylon-12 branch unit.

14. The powder composition of claim 1 , wherein a volume-average particle diameter of the powder composition is between 5 and 100 microns.

15. The powder composition of claim 1 , wherein at least one of the oligomer or polymer arms comprises a reaction product of reactants including a C11-C20 lactam.

16. A method comprising;
providing a polyamide polymer component that includes one or more branched polyamide polymers and is a reaction product of:
a first compound having at least three carboxylic groups; and
a second compound comprising a C11-C20 lactam, a C2-C20 amino acid, or a combination thereof;

forming a laser-sinterable powder that comprises at least 20 weight percent of the polyamide polymer component, wherein the one or more branched polyamide polymers of the polyamide component comprise at least 5 weight percent of the laser-sinterable powder, and wherein the laser-sinterable powder has a melt enthalpy of less than 100 J/g and a sintering window of less than 40° C.

17. The method of claim 16 , further comprising grinding the polyamide polymer component to form the laser-sinterable powder.

18. The method of claim 17 , further comprising melt blending the polyamide polymer component with one or more other materials prior to grinding.

19. A method, comprising:
providing a layer of a sinterable powder composition that comprises:
at least 20 weight percent of a polyamide polymer component,
wherein the polyamide polymer component includes one or more branched polyamide polymers in an amount that comprises at least 5 weight percent of the sinterable powder, and wherein the branched polyamide comprises a star polymer having a single branching unit and at least 3 oligomer or polymer arms covalently attached to the branching unit, wherein the single branching unit is formed from a polycarboxylic acid and at least one of the oligomer or polymer arms comprises a reaction product of reactants including a C11-C20 amino acid, a C11-C20 lactam, or a mixture thereof;

selectively melting at least a portion of the powder layer; and
forming a three-dimensional article by applying one or more additional layers to a preceding layer,
wherein the sinterable powder composition has a melt enthalpy of less than 100 J/g and a sintering window of less than 40° C.

20. The method of claim 19 , further comprising:
using residual powder composition from forming the three-dimensional article in a selective sintering process to produce a second three-dimensional article that does not exhibit orange peel.

21. A three-dimensional article comprising:
a plurality of sintered layers including a polymer matrix;
wherein one or more branched polyamide star polymers comprise at least 5 weight percent of the polymer matrix,
wherein at least one of the star polymers comprises a single branching unit and at least 3 oligomer or polymer arms covalently attached to the branching unit;
wherein the single branching unit is formed from a polycarboxylic acid;
wherein the branched polyamide includes:
a nylon-11 branch unit, a nylon-12 branch unit, or a combination thereof, or
polyamide branch units formed from laurolactam, aminoundecanoic acid, or a mixture thereof; and

wherein the polymer matrix has a melt enthalpy of less than 100 J/g and a sintering window of less than 40° C.

22. A powder composition, comprising:
a laser-sinterable powder that includes at least 40 weight percent of one or more branched polyamide star polymers having a number of average molecular weight of at least 8,000, wherein the one or more branched polyamides include a single branching unit that is attached, via amide linkages, to at least three branch units,
wherein the single branching unit is formed from a polycarboxylic acid,
wherein the branched polyamide includes:
a nylon-11 branch unit, a nylon-12 branch unit, or a combination thereof, or
polyamide branch units formed from laurolactam, aminoundecanoic acid, or a mixture thereof; and

wherein the powder composition has a melt enthalpy of less than 100 J/g and a sintering window of less than 40° C.

Assignees

• Martinoni Raffaele
• Boehler Paul
• Stenson Paul
• SPINDLER JüRGEN
• Kinkelin Eberhard
• Pössnecker Gerhard
• 3D Systems Inc

Inventors

• Martinoni Raffaele
• Boehler Paul
• Stenson Paul
• SPINDLER JüRGEN
• Kinkelin Eberhard
• Pössnecker Gerhard

Classifications

• C08J3/12

  Powdering or granulating · CPC title

• B33Y10/00

  Processes of additive manufacturing · CPC title

• B29B2009/125

  Micropellets, microgranules, microparticles · CPC title

• C08J2377/02

  Polyamides derived from omega-amino carboxylic acids or from lactams thereof (C08J2377/10 takes precedence) · CPC title

• Y10T428/31728

  Next to second layer of polyamide · CPC title