Hydride-coated microparticles and methods for making the same

Patent metadata

Field	Value
Publication number	US-11053575-B2
Application number	US-201816195851-A
Country	US
Kind code	B2
Filing date	Nov 20, 2018
Priority date	May 26, 2014
Publication date	Jul 6, 2021
Grant date	Jul 6, 2021

Abstract

A metal microparticle coated with metal nanoparticles is disclosed. Some variations provide a material comprising a plurality of microparticles (1 micron to 1 millimeter) containing a metal or metal alloy and coated with a plurality of nanoparticles (less than 1 micron) or nanoparticle inclusions (potentially larger than 1 micron). The invention eliminates non-uniform distribution of sintering aids by attaching them directly to the surface of the microparticles. No method is previously known to exist which can assemble nanoparticle inclusions onto the surface of a metal microparticle. Some variations provide a solid article comprising a material with a metal or metal alloy microparticles coated with metal hydride or metal alloy nanoparticles, wherein the nanoparticles form continuous or periodic inclusions at or near grain boundaries within the microparticles.

First claim

What is claimed is:

1. An additively manufactured solid article comprising at least 0.25 wt % of a material containing a plurality of metal-containing or metal alloy-containing microparticles that are at least partially coated with a plurality of metal-containing nanoparticle hydride inclusions, wherein said metal-containing nanoparticle hydride inclusions form a discontinuous coating disposed on said metal-containing or metal alloy-containing microparticles, and wherein said additively manufactured solid article has an equiaxed-grain-growth structure in which said nanoparticle hydride inclusions are nucleation points,
wherein said metal-containing or metal alloy-containing microparticles contain one or more metals selected from the group consisting of Li, Be, Na, Mg, K, Ca, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Fe, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Si, B, C, P, S, Ga, Ge, In, Sn, Sb, Pb, Bi, La, Ac, Ce, Th, Nd, U, and combinations or alloys thereof, and
wherein said metal-containing nanoparticle hydride inclusions contain one or more metals selected from the group consisting of Li, Be, Mg, Ca, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Fe, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Si, B, C, S, Ga, Ge, In, Sn, Sb, Pb, Bi, La, Ac, Ce, Th, Nd, U, and combinations or alloys thereof.

2. The additively manufactured solid article of claim 1 , wherein said additively manufactured solid article has an equiaxed-grain-growth structure.

3. The additively manufactured solid article of claim 1 , wherein said metal-containing nanoparticle hydride inclusions are periodic inclusions at grain boundaries between said metal-containing or metal alloy-containing microparticles.

4. The additively manufactured solid article of claim 1 , wherein said metal-containing or metal alloy-containing microparticles are characterized by an average microparticle size between about 1 micron to about 1 millimeter.

5. The additively manufactured solid article of claim 1 , wherein said metal-containing nanoparticle hydride inclusions are characterized by an average nanoparticle size less than 1 micron.

6. The additively manufactured solid article of claim 1 , wherein the weight ratio of total metals contained in said nanoparticle hydride inclusions divided by total metals contained in said microparticles is between about 0.001 to about 1.

7. The additively manufactured solid article of claim 1 , wherein said metal-containing nanoparticle hydride inclusions are attached to said metal-containing or metal alloy-containing microparticles with organic ligands.

8. The additively manufactured solid article of claim 7 , wherein said organic ligands are selected from the group consisting of aldehydes, alkanes, alkenes, silicones, polyols, poly(acrylic acid), poly(quaternary ammonium salts), poly(alkyl amines), poly(alkyl carboxylic acids), copolymers of maleic anhydride, copolymers of itaconic acid, poly(ethylene imine), poly(propylene imine), poly(vinylimidazoline), poly(trialkylvinyl benzyl ammonium salt), poly(carboxymethylcellulose), poly(D- or L-lysine), poly(L-glutamic acid), poly(L-aspartic acid), poly(glutamic acid), heparin, dextran sulfate, 1-carrageenan, pentosan polysulfate, mannan sulfate, chondroitin sulfate, and combinations or derivatives thereof.

9. The additively manufactured solid article of claim 1 , wherein said additively manufactured solid article comprises at least 50 wt % of said material.

10. The additively manufactured solid article of claim 9 , wherein said additively manufactured solid article comprises at least 95 wt % of said material.

11. The additively manufactured solid article of claim 1 , wherein said additively manufactured solid article is selected from the group consisting of a coating, a billet, and a net shape part.

12. A solid article comprising at least 0.25 wt % of a material containing a plurality of metal-containing or metal alloy-containing microparticles that are at least partially coated with a plurality of metal-containing nanoparticle hydride inclusions, wherein said metal-containing nanoparticle hydride inclusions form a discontinuous coating disposed on said metal-containing or metal alloy-containing microparticles, and wherein said solid article has an equiaxed-grain-growth structure in which said nanoparticle hydride inclusions are nucleation points,
wherein said metal-containing or metal alloy-containing microparticles contain one or more metals selected from the group consisting of Li, Be, Na, Mg, K, Ca, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Fe, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Si, B, C, P, S, Ga, Ge, In, Sn, Sb, Pb, Bi, La, Ac, Ce, Th, Nd, U, and combinations or alloys thereof, and
wherein said metal-containing nanoparticle hydride inclusions contain one or more metals selected from the group consisting of Li, Be, Mg, Ca, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Fe, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Si, B, C, S, Ga, Ge, In, Sn, Sb, Pb, Bi, La, Ac, Ce, Th, Nd, U, and combinations or alloys thereof.

13. The solid article of claim 12 , wherein said article is produced by a process selected from the group consisting of hot pressing, cold pressing and sintering, welding, extrusion, injection molding, additive manufacturing, electron beam melting, selected laser sintering, pressureless sintering, and combinations thereof.

14. The solid article of claim 12 , wherein said solid article is a sintered structure with a porosity between 0% and about 75%.

15. The solid article of claim 12 , wherein said metal-containing nanoparticle hydride inclusions are periodic inclusions at grain boundaries between said metal-containing or metal alloy-containing microparticles.

16. The solid article of claim 12 , wherein said metal-containing or metal alloy-containing microparticles are characterized by an average microparticle size between about 1 micron to about 1 millimeter.

17. The solid article of claim 12 , wherein said metal-containing nanoparticle hydride inclusions are characterized by an average nanoparticle size less than 1 micron.

18. The solid article of claim 12 , wherein the weight ratio of total metals contained in said nanoparticle hydride inclusions divided by total metals contained in said microparticles is between about 0.001 to about 1.

19. The solid article of claim 12 , wherein said metal-containing nanoparticle hydride inclusions are attached to said metal-containing or metal alloy-containing microparticles with organic ligands.

20. The solid article of claim 19 , wherein said organic ligands are selected from the group consisting of aldehydes, alkanes, alkenes, silicones, polyols, poly(acrylic acid), poly(quaternary ammonium salts), poly(alkyl amines), poly(alkyl carboxylic acids) including copolymers of maleic anhydride or itaconic acid, poly(ethylene imine), poly(propylene imine), poly(vinylimidazoline), poly(trialkylvinyl benzyl ammonium salt), poly(carboxymethylcellulose), poly(D- or L-lysine), poly(L-glutamic acid), poly(L-aspartic acid), poly(glutamic acid), heparin, dextran sulfate, 1-carrageenan, pentosan polysulfate, mannan sulfate, chondroitin sulfate, and combinations or derivatives thereof.

Assignees

• Hrl Lab Llc

Inventors

• Martin John H
• Schaedler Tobias A
• Gross Adam F
• Jacobsen Alan J

Classifications

• B22F1/05 Primary

  Metallic powder characterised by the size or surface area of the particles · CPC title

• B22F1/0549

  Hollow particles, including tubes and shells · 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

• B22F1/102

  Metallic powder coated with organic material · CPC title

• B22F1/056

  Submicron particles having a size above 100 nm up to 300 nm · CPC title