Thermoplastic powder material system for appearance models from 3D printing systems

• US 7,569,273 B2
• Filed: 05/19/2004
• Issued: 08/04/2009
• Est. Priority Date: 05/21/2003
• Status: Active Grant

• Current Assignee: 3D Systems, Inc. (3D Systems Corporation)
• Original Assignee: Z CORPORATION (A Holdings Corp.)
• Inventors: Williams, Derek X., DiCologero, Matthew J., Bredt, James F., Clark, Sarah L.
• Primary Examiner(s): Ahmed; Sheeba
• Application Number:
  US10/848,831
• Publication Number:
  US 20050003189A1
• Time in Patent Office: 1,903 Days
• Field of Search: None
• US Class Current: 428/402
• CPC Class Codes: B29C 64/165 using a combination of solid and fluid materials, e.g. a powder selectively bound by a liquid binder, catalyst, inhibitor or energy absorber
• CPC Class Codes: B33Y 70/00 Materials specially adapted for 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: C08L 101/00 Compositions of unspecified macromolecular compounds
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: Y10T 428/25 Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
• CPC Class Codes: Y10T 428/251 Mica
• CPC Class Codes: Y10T 428/252 Glass or ceramic [i.e., fired or glazed clay, cement, etc.] [porcelain, quartz, etc.]
• CPC Class Codes: Y10T 428/253 Cellulosic [e.g., wood, paper, cork, rayon, etc.]
• CPC Class Codes: Y10T 428/254 Polymeric or resinous material
• CPC Class Codes: Y10T 428/256 Heavy metal or aluminum or compound thereof
• CPC Class Codes: Y10T 428/257 Iron oxide or aluminum oxide
• CPC Class Codes: Y10T 428/258 Alkali metal or alkaline earth metal or compound thereof
• CPC Class Codes: Y10T 428/259 Silicic material
• CPC Class Codes: Y10T 428/2982 Particulate matter [e.g., sphere, flake, etc.]

Abstract

A materials system and method is provided to enable the formation of articles by three-dimensional printing. The materials system includes thermoplastic particulate filler material that allows the accurate definition of articles that are strong without being brittle.

Claims

1. A powder adapted for three-dimensional printing, the powder comprising:

a loose and free-flowing particulate mixture comprising;

a thermoplastic particulate material selected from the group consisting of acetal polyoxymethylene, polylactide, ethylene vinyl acetate, polyphenylene ether, ethylene-acrylic acid copolymer, polyether block amide, polyvinylidene fluoride, polyetherketone, polybutylene terephthalate, polyethylene terephthalate, polycyclohexylenemethylene terephthalate, polyphenylene sulfide, polythalamide, polymethylmethacrylate, polysulfones, polyethersulfones, polyphenylsulfones, polyacrylonitrile, poly(acrylonitrile-butadiene-styrene), polyamides, polystyrene, polyolefin, polyvinyl butyral, polycarbonate, polyvinyl chlorides, ethyl cellulose, cellulose acetate cellulose xanthate, and combinations, and copolymers thereof; and

an adhesive particulate material comprising a water-soluble resin including at least one of sulfonated polyester polymer, sulfonated polystyrene, polyethylene oxide, butylated polyvinylpyrrolidone, polyvinyl alcohol-co-vinyl acetate, cationic starch, pregelatinized cationic starch, or combinations or copolymers thereof,

wherein the adhesive particulate material is adapted to bond the thermoplastic particulate material when a fluid activates the adhesive particulate material.

2. The powder of claim 1 wherein the fluid is aqueous.

3. The powder of claim 1 wherein the fluid is adapted to be solidifiable by exposure to at least one of ultraviolet light, visible light, or electron beam, and combinations thereof.

4. The powder of claim 1 wherein the fluid is non-aqueous and non-halogenated.

5. The powder of claim 1 wherein the thermoplastic particulate material comprises particles having a mean particle diameter of about 10 micrometers to about 100 micrometers.

6. The powder of claim 1 wherein the adhesive particulate material comprises particles having a mean particle diameter of about 10 micrometers to about 100 micrometers.

7. The powder of claim 1 wherein-the fluid activates the adhesive particulate material by dissolving the adhesive particulate material.

8. The powder of claim 1 further comprising:

a filler material.

9. The powder of claim 8 wherein the filler material comprises an inorganic material.

10. The powder of claim 9 wherein the inorganic material is selected from the group consisting of aluminum oxide, soda-lime glass, borosilicate glass, silica, aluminosilicate ceramic, limestone, plaster, bentonite, precipitated sodium silicate, amorphous precipitated silica, amorphous precipitated calcium silicate, amorphous precipitated magnesium silicate, amorphous precipitated lithium silicate, salt, aluminum hydroxide, magnesium hydroxide, calcium phosphate, sand, wollastonite, dolomite, amorphous precipitated silicates comprising at least two ions selected from the group consisting of sodium ions, lithium ions, magnesium ions, and calcium ions, and combinations thereof.

11. The powder of claim 8 wherein the filler material comprises an organic material.

12. The powder of claim 11 wherein the organic material comprises a carbohydrate.

13. The powder of claim 12 wherein the carbohydrate is selected from the group consisting of modified starch, cellulose,-acacia gum, locust bean gum, pregelatinized starch, acid-modified starch, hydrolyzed starch, sodium carboxymethylecellulose, sodium alginate, hydroxypropyl cellulose, methyl cellulose, chitosan, carrageenan, pectin, agar, gellan gum, gum Arabic, xanthan gum, propylene glycol alginate, guar gum, and combinations thereof.

14. The powder of claim 1, further comprising:

a processing aid material.

15. The powder of claim 1, further comprising:

a reinforcing fiber.

16. The powder of claim 1, further comprising:

a filler material; and

a processing aid material.

17. An article comprising:

a product of;

a powder comprising a loose and free-flowing particulate mixture comprising;

(i) a thermoplastic particulate material selected from the group consisting of acetal polyoxymethylene, polylactide, ethylene vinyl acetate, polyphenylene ether, ethylene-acrylic acid copolymer, polyether block amide, polyvinylidene fluoride, polyetherketone, polybutylene terephthalate, polyethylene terephthalate, polycyclohexylenemethylene terephthalate, polyphenylene sulfide, polythalamide, polymethylmethacrylate, polysulfones, polyethersulfones, polyphenylsulfones, polyacrylonitrile, poly(acrylonitrile-butadiene-styrene), polyamides, polystyrene, polyolefin, polyvinyl butyral, polycarbonate, polyvinyl chlorides, ethyl cellulose, cellulose acetate cellulose xanthate, and combinations, and copolymers thereof, and

(ii) an adhesive particulate material selected from the group consisting of a resin and an inorganic adhesive; and

a fluid that activates the adhesive particulate material to form a substantially solid article composed of the powder, the adhesive particulate material being substantially soluble in the fluid,

wherein the article includes a plurality of adjacent layers formed by the product, each layer having a contour defining an edge, and a final shape of the article being defined by respective edges of the layers and the adhesive particulate material is selected from the group consisting of (i) an inorganic adhesive including at least one of magnesium phosphate cement, magnesium oxychloride cement, magnesium oxysulfate cement, zinc phosphate cement, zinc oxide-eugenol cement, or combinations thereof, (ii) an alkaline-reducible resin including at least one of octylacrylamide/acrylate/butylaminoethyl methacrylate copolymer, acrylates/octylacrylamide copolymer, styrenated polyacrylic acid, or combinations or copolymers thereof, and (iii) a water-soluble resin including at least one of sulfonated polyester polymer, sulfonated polystyrene, polyethylene oxide, butylated polyvinylpyrrolidone, polyvinyl alcohol-co-vinyl acetate, cationic starch, pregelatinized cationic starch, or combinations or copolymers thereof.

18. A method for forming an article by three-dimensional printing, the method comprising the steps of:

providing a plurality of adjacent particles having a mean diameter of about 10 micrometers to about 100 micrometers, the particles comprising a loose and free-flowing blend of a thermoplastic particulate material and an adhesive particulate material; and

applying to the plurality of particles a fluid, within which the adhesive particulate material is at least partially soluble and the thermoplastic particulate material is substantially inert, the fluid activating the adhesive particulate material from a substantially inert state, in an amount sufficient to bond the plurality of particles together to define a substantially solid, singular article,

wherein the thermoplastic particulate material is selected from the group consisting of acetal polyoxymethylene, polylactide, ethylene vinyl acetate, polyphenylene ether, ethylene-acrylic acid copolymer, polyether block amide, polyvinylidene fluoride, polyetherketone, polybutylene terephthalate, polyethylene terephthalate, polycyclohexylenemethylene terephthalate, polyphenylene sulfide, polythalamide, polymethylmethacrylate, polysulfones, polyethersulfones, polyphenylsulfones, polyacrylonitrile, poly(acrylonitrile-butadiene-styrene), polyamides, polystyrene, polyolefin, polyvinyl butyral, polycarbonate, polyvinyl chlorides, ethyl cellulose, cellulose acetate cellulose xanthate, and combinations, and copolymers thereof.

19. The method of claim 18 further comprising the step of heating the article to at least partially sinter the thermoplastic particulate material.

20. A method for forming an article by three-dimensional printing, the method comprising the steps of:

providing a plurality of adjacent particles having a mean diameter of about 10 micrometers to about 100 micrometers, the particles comprising a loose and free-flowing particulate mixture comprising a blend of a thermoplastic particulate material and an adhesive particulate material; and

applying to the plurality of particles a fluid, within which the adhesive particulate material is at least partially soluble and the thermoplastic particulate material is substantially inert, the fluid dissolving the adhesive particulate material, in an amount sufficient to bond the plurality of particles together to define a substantially solid, singular article,

wherein the thermoplastic particulate material is selected from the group consisting of acetal polyoxymethylene, polylactide, ethylene vinyl acetate, polyphenylene ether, ethylene-acrylic acid copolymer, polyether block amide, polyvinylidene fluoride, polyetherketone, polybutylene terephthalate, polyethylene terephthalate, polycyclohexylenemethylene terephthalate, polyphenylene sulfide, polythalamide, polymethylmethacrylate, polysulfones, polyethersulfones, polyphenylsulfones, polyacrylonitrile, poly(acrylonitrile-butadiene-styrene), polyamides, polystyrene, polyolefin, polyvinyl butyral, polycarbonate, polyvinyl chlorides, ethyl cellulose, cellulose acetate cellulose xanthate, and combinations, and copolymers thereof.

21. The method of claim 20, further comprising the step of heating the article to at least partially sinter the thermoplastic particulate material.

22. A method for forming an article by three-dimensional printing, the method comprising the steps of:

applying, to a first portion of a first film of a loose and free-flowing particulate mixture including a thermoplastic particulate material and an activatable adhesive particulate material, an aqueous fluid that activates the adhesive in an amount sufficient to form an essentially solid, singular article of adhered particles;

forming a second film of the particles on the first film; and

applying, to a first portion of the second film of particles, the aqueous fluid in an amount sufficient to activate the adhesive to the extent that the particles within the first portion of the second film adhere to each other and to at least a portion of the first portion of the first film to form an essentially solid, singular article from the first portion of the first film and the first portion of the second film,

wherein the thermoplastic particulate material is selected from the group consisting of acetal polyoxymethylene, polylactide, ethylene vinyl acetate, polyphenylene ether, ethylene-acrylic acid copolymer, polyether block amide, polyvinylidene fluoride, polyetherketone, polybutylene terephthalate, polyethylene terephthalate, polycyclohexylenemethylene terephthalate, polyphenylene sulfide, polythalamide, polymethylmethacrylate, polysulfones, polyethersulfones, polyphenylsulfones, polyacrylonitrile, poly(acrylonitrile-butadiene-styrene), polyamides, polystyrene, polyolefin, polyvinyl butyral, polycarbonate, polyvinyl chlorides, ethyl cellulose, cellulose acetate cellulose xanthate, and combinations, and copolymers thereof.

23. The method of claim 22, further comprising the step of heating the article to at least partially sinter the thermoplastic particulate material.

24. A method for forming an essentially solid, singular article by three-dimensional printing, the method comprising the steps of:

applying, to a first portion of a first film of particles that includes a plurality of thermoplastic particles, a non-aqueous fluid that activates the surface of the thermoplastic particles in an amount sufficient to form a structure of adhered particles, defining a first cross-sectional portion of the article;

forming a second film of the particles on the first film;

applying, to a first portion of the second film of particles, the non-aqueous fluid in an amount sufficient to activate the surface of the thermoplastic particles to the extent that the particles within the first portion of the second film adhere to each other and to at least a portion of the first portion of the first film to define a second cross-sectional portion of the article including-the first portion of the first film and the first portion of the second film; and

thereafter, applying at least one of an ultraviolet light, visible light, or an electron beam on the printed cross-sectional portions to induce the non-aqueous fluid to solidify.

25. A powder adapted for three-dimensional printing, the powder comprising:

a loose and free-flowing particulate mixture comprising;

a thermoplastic particulate material selected from the group consisting of acetal polyoxymethylene, polylactide, ethylene vinyl acetate, polyphenylene ether, ethylene-acrylic acid copolymer, polyether block amide, polyvinylidene fluoride, polyetherketone, polybutylene terephthalate, polyethylene terephthalate, polycyclohexylenemethylene terephthalate, polyphenylene sulfide, polythalamide, polymethylmethacrylate, polysulfones, polyethersulfones, polyphenylsulfones, polyacrylonitrile, poly(acrylonitrile-butadiene-styrene), polyamides, polystyrene, polyolefin, polyvinyl butyral, polycarbonate, polyvinyl chlorides, ethyl cellulose, cellulose acetate cellulose xanthate, and combinations, and copolymers thereof; and

an adhesive particulate material selected from the group consisting of (i) an inorganic adhesive including at least one of magnesium phosphate cement, magnesium oxychloride cement, magnesium oxysulfate cement, zinc phosphate cement, zinc oxide eugenol cement, or combinations thereof, and (ii) an alkaline-reducible resin including at least one of octylacrylamide/acrylate/butylaminoethyl methacrylate copolymer, acrylates/octylacrylamide copolymer, styrenated polyacrylic acid, or combinations or copolymers thereof,

wherein the adhesive particulate material is adapted to bond the thermoplastic particulate material when a fluid activates the adhesive particulate material.

26. The powder of claim 25 wherein the fluid is aqueous.

27. The powder of claim 25 wherein the fluid that activates the thermoplastic particulate material is adapted to be solidifiable by exposure to at least one of ultraviolet light, visible light, or electron beam, and combinations thereof.

28. The powder of claim 25 wherein the fluid is non-aqueous and non-halogenated.

29. The powder of claim 25 wherein the thermoplastic particulate material comprises particles having a mean particle diameter of about 10 micrometers to about 100 micrometers.

30. The powder of claim 25 wherein the adhesive particulate material comprises particles having a mean particle diameter of about 10 micrometers to about 100 micrometers.

31. The powder of claim 25, wherein the adhesive particulate material comprises the inorganic adhesive.

32. The powder of claim 25 wherein the adhesive particulate material comprises the alkaline-reducible resin.

33. The powder of claim 25, further comprising a filler material.

34. The powder of claim 33 wherein the filler material comprises an inorganic material.

35. The powder of claim 34 wherein the inorganic material is selected from the group consisting of aluminum oxide, soda-lime glass, borosilicate glass, silica, aluminosilicate ceramic, limestone, plaster, bentonite, precipitated sodium silicate, amorphous precipitated silica, amorphous precipitated calcium silicate, amorphous precipitated magnesium silicate, amorphous precipitated lithium silicate, salt, aluminum hydroxide, magnesium hydroxide, calcium phosphate, sand, wollastonite, dolomite, amorphous precipitated silicates comprising at least two ions selected from the group consisting of sodium ions, lithium ions, magnesium ions, and calcium ions, and combinations thereof.

36. The powder of claim 33 wherein the filler material comprises an organic material.

37. The powder of claim 36 wherein the organic material comprises a carbohydrate.

38. The powder of claim 37 wherein the carbohydrate is selected from the group consisting of modified starch, cellulose, acacia gum, locust bean gum, pregelatinized starch, acid-modified starch, hydrolyzed starch, sodium carboxymethylecellulose, sodium alginate, hydroxypropyl cellulose, methyl cellulose, chitosan, carrageenan, pectin, agar, gellan gum, gum Arabic, xanthan gum, propylene glycol alginate, guar gum, and combinations thereof.

39. The powder of claim 25, further comprising a processing aid material.

40. The powder of claim 25, further comprising a reinforcing fiber.

41. The powder of claim 25, further comprising:

a filler material; and

a processing aid material.