Resin formulations for additive manufacturing of metals, and methods of making and using the same

Patent metadata

Field	Value
Publication number	US-11591484-B1
Application number	US-201916672385-A
Country	US
Kind code	B1
Filing date	Nov 1, 2019
Priority date	Jan 30, 2019
Publication date	Feb 28, 2023
Grant date	Feb 28, 2023

Abstract

Some variations provide a composition for additive manufacturing (3D printing) of metals, comprising: from 10 vol % to 70 vol % of a photocurable liquid resin; from 10 vol % to 70 vol % of metal or metal alloy particles, optionally configured with a photoreflective surface; and from 0.01 vol % to 10 vol % of a photoinitiator. Other variations provide a composition for additive manufacturing of metals, comprising: from 1 vol % to 70 vol % of a photocurable liquid resin; from 0.1 vol % to 98 vol % of an organometallic compound containing a first metal; from 1 vol % to 70 vol % of metal or metal alloy particles containing a second metal (which may be the same as or different than the first metal); and from 0.01 vol % to 10 vol % of a photoinitiator. Many examples of metals, photocurable resins, organometallic compounds, photoinitiators, and optional additives are disclosed, and methods of making and using the composition are described.

First claim

What is claimed is:

1. A composition for additive manufacturing of metals, said composition comprising:
(a) from about 10 vol % to about 70 vol % of a photocurable liquid resin, wherein said photocurable liquid resin contains an organometallic resin component selected from metal-coordination monomers, oligomers, polymers, or combinations thereof;
(b) from about 10 vol % to about 70 vol % of metal or metal alloy particles, wherein said metal or metal alloy particles are optionally configured with a photoreflective surface; and
(c) from about 0.01 vol % to about 10 vol % of a photoinitiator.

2. The composition of claim 1 , wherein said photocurable liquid resin contains one or more acrylates, methacrylates, thiols, vinyls, allyls, alkenes, alkynyls, epoxies, combinations thereof, or reaction products thereof.

3. The composition of claim 1 , wherein said photocurable liquid resin contains a component containing a C═X and/or C≡X bond, wherein X is selected from C, S, O, and/or N.

4. The composition of claim 1 , wherein said photocurable liquid resin contains an organic resin component selected from the group consisting of acrylic acid, poly(ethylene-co-methacrylic acid), poly(ethylene-co-acrylic acid), 1,6-hexanediol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetrakis(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate), 1,3,5-triallyl-1, 3,5-triazine-2,4,6(1H,3H,5H)-trione, and combinations thereof.

5. The composition of claim 4 , wherein said organic resin component is present in a concentration from about 10 vol % to about 80 vol % of said photocurable liquid resin.

6. The composition of claim 1 , wherein said organometallic resin component is present in a concentration from about 10 vol % to about 50 vol % of said photocurable liquid resin.

7. The composition of claim 1 , wherein said organometallic resin component is selected from the group consisting of nickel acrylate, cobalt acrylate, copper acrylate, iron acrylate, zinc acrylate, aluminum acrylate, nickel methacrylate, cobalt methacrylate, copper methacrylate, iron methacrylate, zinc methacrylate, aluminum methacrylate, and combinations thereof.

8. The composition of claim 1 , wherein said organometallic resin component is selected from the group consisting of potassium trichloro(ethene)platinate, potassium trichloro(ethene)palladiumate, potassium trichloro(ethene)nickelate, bis(cyclooctadiene)nickel(0), iron cyclooctatetraene, transition-metal fullerene complexes, metal acetylacetonates, and combinations thereof.

9. The composition of claim 1 , wherein said metal or metal alloy particles are surface-polished to provide said photoreflective surface.

10. The composition of claim 1 , wherein said metal or metal alloy particles are coated with a photoreflective coating that has a surface composition that is different than the composition of said metal or metal alloy particles.

11. The composition of claim 10 , wherein said surface composition of said photoreflective coating includes a metal selected from the group consisting of Ni, Cu, Co, Fe, and combinations thereof.

12. The composition of claim 10 , wherein the thickness of said photoreflective coating is from about 100 nanometers to about 2000 nanometers.

13. The composition of claim 1 , wherein said metal or metal alloy particles are characterized by an average effective diameter from about 0.5 microns to about 20 microns.

14. The composition of claim 1 , wherein said metal or metal alloy particles are characterized by an average aspect ratio greater than 1.

15. The composition of claim 10 , wherein said metal or metal alloy particles are characterized by an average effective diameter from about 0.5 microns to about 20 microns, wherein the thickness of said photoreflective coating is from about 100 nanometers to about 2000 nanometers, and wherein said surface composition of said photoreflective coating includes a metal selected from the group consisting of Ni, Cu, Co, Fe, and combinations thereof.

16. The composition of claim 1 , wherein said metal or metal alloy particles contain a metal selected from the group consisting of Ni, Cu, Co, Fe, Mn, V, Cr, Ti, Al, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, La, Hf, Ta, W, Re, Os, Ir, Pt, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and combinations thereof.

17. The composition of claim 1 , wherein said metal or metal alloy particles contain a metal alloy selected from the group consisting of aluminum alloys, stainless steels, high-temperature steels, nickel alloys comprising Ni, Al, and Cr with more than 3 wt % Al and a Cr/Al ratio less than 4, nickel alloys comprising Ni, Al, and Cr with more than 10 wt % Cr and a Cr/Al ratio greater than 4, and combinations thereof.

18. The composition of claim 1 , wherein said photoinitiator is present in a concentration from about 0.1 vol % to about 5 vol %.

19. The composition of claim 1 , wherein said photoinitiator is selected from the group consisting of 2,2-dimethoxy-2-phenylacetophenone; 2-hydroxy-2-methylpropiophenone; camphorquinone; bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide; diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide; benzophenone; azobisisobutyronitrile; peroxides; benzoyl peroxide; thioxanthones; and combinations thereof.

20. The composition of claim 1 , said composition further comprising from about 0.01 vol % to about 25 vol % of a UV reflector containing a metal selected from the group consisting of Al, Co, Cu, Ag, Au, Ca, In, K, Li, Mg, Na, Rb, Zn, and combinations thereof.

21. The composition of claim 1 , said composition further comprising from about 1 vol % to about 50 vol % of a solvent selected from the group consisting of isopropyl alcohol, ethanol, methoxyethanol, dimethylformamide, ethyl acetate, dichloromethane, dimethylsulfoxide, acetonitrile, chloroform, tetrahydrofuran, and combinations thereof.

22. The composition of claim 1 , said composition further comprising from about 0.01 vol % to about 5 vol % of a surfactant.

23. The composition of claim 1 , said composition further comprising from about 0.01 vol % to about 25 vol % of a sinter aid.

24. The composition of claim 1 , said composition further comprising from about 0.01 vol % to about 10 vol % of a 3D-printing resolution agent.

25. A composition for additive manufacturing of metals, said composition comprising:
(a) from about 1 vol % to about 70 vol % of a photocurable liquid resin;
(b) from about 0.1 vol % to about 98 vol % of an organometallic compound containing a first metal;
(c) from about 1 vol % to about 70 vol % of metal or metal alloy particles, wherein said metal or metal alloy particles contain a second metal; and
(d) from about 0.01 vol % to about 10 vol % of a photoinitiator.

26. The composition of claim 25 , wherein said photocurable liquid resin contains one or more acrylates, methacrylates, thiols, vinyls, allyls, alkenes, alkynyls, epoxies, combinations thereof, or reaction products thereof.

27. The composition of claim 25 , wherein said photocurable liquid resin contains a component containing a C═X and/or C≡X bond, wherein X is selected from C, S, O, and/or N.

28. The composition of claim 25 , wherein said photocurable liquid resin contains a resin organic component selected from the group consisting of acrylic acid, poly(ethylene-co-methacrylic acid), poly(ethylene-co-acrylic acid), 1,6-hexaned

Assignees

• Hrl Lab Llc

Inventors

• Schaedler Tobias A
• Bui Phuong P
• Eckel Zak C
• Hundley Jacob M
• Porter Kayleigh A
• Martin John H

Classifications

• B22F2998/00

  Supplementary information concerning processes or compositions relating to powder metallurgy · CPC title

• B22F10/12

  by photopolymerisation, e.g. stereolithography [SLA] or digital light processing [DLP] · CPC title

• B22F1/17

  Metallic particles coated with metal · CPC title

• B22F1/16

  Metallic particles coated with a non-metal (coated with lubricating or binding agents or with organic material B22F1/10) · CPC title

• B22F1/145

  Chemical treatment, e.g. passivation or decarburisation · CPC title