Surface modified particulate and sintered or injection molded products

• US 10,052,691 B2
• Filed: 05/12/2016
• Issued: 08/21/2018
• Est. Priority Date: 07/11/2013
• Status: Active Grant

• Current Assignee: Tundra Composites, LLC.
• Original Assignee: Tundra Composites, LLC.
• Inventors: Heikkila, Kurt E.
• Primary Examiner(s): Cain, Edward J
• Application Number:
  US15/152,772
• Publication Number:
  US 20160256925A1
• Time in Patent Office: 831 Days
• CPC Class Codes: B22F 1/062 Fibrous particles
• CPC Class Codes: B22F 1/065 Spherical particles
• CPC Class Codes: B22F 1/0655 Hollow particles
• CPC Class Codes: B22F 1/10 Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
• CPC Class Codes: B22F 1/102 Metallic powder coated with organic material
• CPC Class Codes: B22F 1/107 containing organic material comprising solvents, e.g. for slip casting
• CPC Class Codes: B22F 10/00 Additive manufacturing of workpieces or articles from metallic powder apparatus or devices therefor B22F12/00
• CPC Class Codes: B22F 10/12 by photopolymerisation, e.g. stereolithography [SLA] or digital light processing [DLP]
• CPC Class Codes: B22F 10/18 by mixing binder with metal in filament form, e.g. fused filament fabrication [FFF]
• CPC Class Codes: B22F 10/28 Powder bed fusion, e.g. selective laser melting [SLM] or electron beam melting [EBM]
• CPC Class Codes: B22F 10/40 Structures for supporting workpieces or articles during manufacture and removed afterwards
• CPC Class Codes: B22F 12/53 Nozzles
• CPC Class Codes: B22F 2201/01 Reducing atmosphere
• CPC Class Codes: B22F 2302/45 Others, including non-metals
• CPC Class Codes: B22F 2304/10 Micron size particles, i.e. above 1 micrometer up to 500 micrometer
• CPC Class Codes: B22F 2998/10 Processes characterised by the sequence of their steps
• CPC Class Codes: B22F 3/004 Filling molds with powder feeding material to presses in general B30B15/302
• CPC Class Codes: B22F 3/1021 Removal of binder or filler removal of binder from ceramics C04B35/638
• CPC Class Codes: B22F 3/16 in successive or repeated steps
• CPC Class Codes: B22F 3/20 by extruding
• CPC Class Codes: B22F 3/225 : by injection molding
• CPC Class Codes: B22F 5/12 : of wires of tubes B22F5/10
• CPC Class Codes: B28B 1/001 : Rapid manufacturing of 3D objects by additive depositing, agglomerating or laminating of material selective deposition modelling of metallic powder B22F10/00; rapid manufacturing of 3D objects in general and in particular of plastics B29C64/00
• CPC Class Codes: B29C 2948/92704 : Temperature
• CPC Class Codes: B29C 48/022 : characterised by the choice of material
• CPC Class Codes: B29C 48/05 : Filamentary, e.g. strands
• CPC Class Codes: B29C 48/155 : Partial coating thereof
• CPC Class Codes: B29C 48/86 : at the nozzle zone
• CPC Class Codes: B29C 48/92 : Measuring, controlling or regulating
• CPC Class Codes: B29C 64/106 : using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
• CPC Class Codes: B29C 64/118 : using filamentary material being melted, e.g. fused deposition modelling [FDM]
• CPC Class Codes: B29K 2023/065 : HDPE, i.e. high density polyethylene
• CPC Class Codes: B29K 2505/12 : Iron
• CPC Class Codes: B33Y 10/00 : Processes of additive manufacturing
• CPC Class Codes: B33Y 70/10 : Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
• CPC Class Codes: C08K 2003/0856 : Iron
• CPC Class Codes: C08K 2201/005 : Additives being defined by their particle size in general
• CPC Class Codes: C08K 2201/01 : Magnetic additives
• CPC Class Codes: C08K 3/08 : Metals
• CPC Class Codes: C08K 3/34 : Silicon-containing compounds
• CPC Class Codes: C08K 3/40 : Glass
• CPC Class Codes: C08K 7/28 : Glass
• CPC Class Codes: C08K 9/04 : Ingredients treated with organic substances treated with macromolecular compounds C08K9/08
• CPC Class Codes: C08L 23/06 : Polyethene
• CPC Class Codes: C22C 32/0094 : with organic materials as the main non-metallic constituent, e.g. resin
• CPC Class Codes: D01F 1/10 : Other agents for modifying properties
• CPC Class Codes: D01F 6/04 : from polyolefins
• CPC Class Codes: D01F 6/46 : of polyolefins
• CPC Class Codes: D01F 9/08 : of inorganic material working or processing of metal wire B21F; from softened glass, minerals or slags C03B37/00
• CPC Class Codes: D10B 2321/02 : polyolefins
• CPC Class Codes: D10B 2321/021 : polyethylene
• CPC Class Codes: H01F 1/28 : dispersed or suspended in a bonding agent
• CPC Class Codes: Y02P 10/25 : Process efficiency
• CPC Class Codes: Y10T 428/2927 : including structurally defined particulate matter

Abstract

Disclosed are interfacially modified particulate and polymer composite material for use in injection molding processes, such as metal injection molding and additive process such as 3D printing. The composite material is uniquely adapted for powder metallurgy processes. Improved products are provided under process conditions through surface modified powders that are produced by extrusion, injection molding, additive processes such as 3D printing, Press and Sinter, or rapid prototyping.

Claims

1. An article adapted for use in an additive manufacturing system, the system comprising a digitally controlled applicator that can deposit a filament in a controlled x-y plane and in a z-direction filament application to obtain a pre-form object;

the article comprising a filament, having a diameter of about 0.1 to 3 millimeters, comprising a thermoplastic composite comprising;

(a) about 70 to 1 wt. % of a thermoplastic polymer; and

(b) about 99 to 30 wt. % of a metal particulate, dispersed in the polymer, particulate having a particle size of less than 500 microns, and the particulate having exterior coating of interfacial modifier in an amount of about 0.005 to 10.0 wt. %, all percentages based on the weight of the filament.

2. The article of claim 1 wherein the metal particulate comprises a blend of a first particulate and a second particulate.

3. The article of claim 2 wherein the first particulate has a particle size less than 100μ

and the second particulate has a particle size greater than 100μ

.

4. The article of claim 1 wherein the filament comprises a ferrous metal particulate dispersed in a polyolefin.

5. The article of claim 4 wherein the filament comprises a stainless steel particulate dispersed in a high-density polyethylene.

6. The article of claim 1 wherein the filament comprises a generally circular cross-section with a diameter of about 0.1 to 2 millimeters.

7. The article of claim 1 wherein the interfacial modifier comprises an organometallic compound selected from the group of organo-titanium compound, organo-zirconium compound or mixtures thereof.

8. An article adapted for use in an additive manufacturing system, the system comprising a digitally controlled applicator that can deposit a filament in a controlled x-y plane with subsequent z-direction filament application to obtain a pre-form object;

the article comprising filament having a diameter of about 0.11 to 3 millimeters, the filament comprising a thermoplastic composition comprising;

(a) about 70 to 1 wt. % of a thermoplastic polymer; and

(b) about 99 to 30 wt. % of a particulate selected from a ceramic particulate, an inorganic particulate or a glass particulate dispersed in the polymer, particulate having a particle size of less than 500 microns; and

the particulate having an exterior coating of interfacial modifier in an amount of about 0.005 to 10.0 wt. %, all percentages based on the weight of the filament.

9. The article of claim 8 wherein the particulate comprises a blend of a first particulate and a second particulate.

10. The article of claim 9 wherein the first particulate has a particle size less than 100μ

and the second particle particulate has a particle size greater than 100μ

.

11. The article of claim 8 wherein the thermoplastic polymer comprises a polyolefin.

12. The article of claim 11 wherein the filament comprises a high-density polyethylene and the particulate comprises a magnetic particulate, a glass sphere particulate, a glass micro-bubble particulate or mixtures thereof.

13. The article of claim 8 wherein the filament comprises a generally circular cross-section with a diameter of about 0.1 to 2 millimeters.

14. The article of claim 8 wherein the interfacial modifier comprises an organometallic compound selected from the group of organo-titanium compound, organo-zirconium compound or mixtures thereof.

15. An article adapted for use in an additive manufacturing system, the system comprising a digitally controlled applicator that can deposit a filament in a controlled x-y plane and in a z-direction filament application to obtain a pre-form object;

the article comprising a filament, having a diameter of about 0.1 to 3 millimeters, comprising a thermoplastic composite comprising;

(a) about 70 to 1 wt. % of a thermoplastic polymer; and

(b) about 99 to 50 wt. % of a metal particulate comprising copper, iron or titanium, dispersed in the polymer, particulate having a particle size of 4 to 200 microns, and the particulate having exterior coating of interfacial modifier in an amount of about 0.005 to 10.0 wt. %, all percentages based on the weight of the filament;

wherein in the filament the composite has a volume packing greater than 75%.

16. The article of claim 15 wherein the particulate comprises steel.

17. The article of claim 16 wherein the particulate comprises stainless steel.

18. The article of claim 15 wherein the particulate comprises a titanium alloy.

19. The article of claim 15 wherein the particulate comprises a bronze.

20. The article of claim 15 wherein the volume packing is greater than 80%.

21. The article of claim 15 wherein the volume packing is greater than 85%.

22. The article of claim 15 wherein the composite comprises about 99 to 60 wt. % metal particulate.

23. The article of claim 15 wherein the metal particulate comprises a blend of a first particulate and a second particulate.