Surface modified particulate and sintered or injection molded products

• US 10,456,836 B2
• Filed: 10/12/2016
• Issued: 10/29/2019
• Est. Priority Date: 07/11/2013
• Status: Active Grant

• Current Assignee: Tundra Composites, LLC.
• Original Assignee: Tundra Composites, LLC.
• Inventors: Heikkila, Kurt
• Primary Examiner(s): Cain, Edward J
• Application Number:
  US15/291,727
• Publication Number:
  US 20170028475A1
• Time in Patent Office: 1,112 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. A method of making a shaped metal or inorganic object with an additive manufacturing system, the method comprises

depositing successive layers of a filament on a build bed or a platform;

forming a shape from a digital model, the system comprising a digitally controlled applicator, in a controlled x-y plane with z-direction filament application to obtain a preform object;

the filament comprising a composite of about 70 to 1 wt. % of a thermoplastic polymer; and

about 99 to 30 wt. % of a particulate, dispersed in the polymer, the particulate having a particle size of less than 500 microns and an exterior coating of interfacial modifier on the particulate in an amount of about 0.02 to 2.0 wt. %, all percentages based on the weight of the composite; and

sintering the preform object to remove the polymer and to bond the particulate forming the shaped metal or inorganic object;

wherein the particulate comprises a metal alloy particle, an inorganic particle, a ceramic particle, a bi-metal particle or blends thereof.

2. The method of claim 1 wherein the ceramic particle is a tungsten carbide.

3. The method of claim 1 wherein the alloy particle is a stainless steel.

4. The method of claim 1 wherein the ceramic particle is a glass sphere.

5. The method of claim 4 wherein the glass sphere is a hollow sphere.

6. The method of claim 4 wherein the glass sphere is a solid sphere.

7. The method of claim 1 wherein the bi-metal particle comprises at least copper, iron, nickel, tungsten or molybdenum.

8. The method of claim 1 wherein the preform object is mechanically shaped prior to sintering.

9. The method of claim 1 wherein the preform object is sintered at a temperature greater than about 1000°

C.

10. The method of claim 9 wherein in sintering the preform object, the preform object is sintered by increasing the temperature at a rate greater than 100°

C. per hour beginning at an initial temperature.

11. The method of claim 10 wherein the initial temperature is less than 100°

C.

12. The method of claim 1 wherein the preform object comprises a first filament and a second filament the second filament comprising either a particulate or a polymer different than the first filament.

13. The method of claim 1 wherein the sintering is conducted in a reducing atmosphere.

14. The method of claim 1 wherein the preform object has a volume packing of the particulate of greater than 85%.