Three dimensional printing material system and method

• US 7,332,537 B2
• Filed: 08/26/2003
• Issued: 02/19/2008
• Est. Priority Date: 09/04/1996
• Status: Expired due to Term

• Current Assignee: 3D Systems, Inc. (3D Systems Corporation)
• Original Assignee: Z CORPORATION (A Holdings Corp.)
• Inventors: Anderson, Timothy C., Bredt, James F., Russell, David B.
• Primary Examiner(s): SHOSHO, CALLIE E
• Application Number:
  US10/650,086
• Publication Number:
  US 20040138336A1
• Time in Patent Office: 1,638 Days
• Field of Search: 523/160, 264/401
• US Class Current: 524/423
• CPC Class Codes: B28B 1/00 Producing shaped prefabricated articles from the material using presses B28B3/00; shaping on moving conveyors B28B5/00; producing tubular articles B28B21/00 ; producing articles with embedded elements B28B23/00
• 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: B28B 7/465 Applying setting liquid to dry mixtures
• CPC Class Codes: B29C 41/003 characterised by the choice of material
• 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: B29C 67/243 for making articles of definite length
• CPC Class Codes: B29K 2105/0097 Glues or adhesives, e.g. hot melts or thermofusible adhesives
• CPC Class Codes: B29K 2105/16 Fillers
• CPC Class Codes: B29K 2995/0059 Degradable
• 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: C04B 2111/00181 Mixtures specially adapted for three-dimensional printing (3DP), stereo-lithography or prototyping
• CPC Class Codes: C04B 28/14 containing calcium sulfate cements gypsum-paper plates E04C
• CPC Class Codes: C04B 40/00 Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability active ingredients C04B22/00 - C04B24/00; hardening of a well-defined composition C04B26/00 - C04B28/00; making porous, cellular or lightening C04B38/00; mechanical aspects B28, e.g. conditioning the materials prior to shaping B28B17/02

Abstract

The present invention is directed to a 3DP™ material composition and method of use. The composition of the present invention includes an adhesive material, a fibrous component and a filler. Alternatively, the composition may include a particulate material having a mean particle size between about 10 microns and about 300 microns, a soluble adhesive material. The compositions may also include an accelerator and an additional adhesive.

Claims

1. A three dimensional printing composition, comprising:

a dry, loose, free-flowing particulate material including;

about 10% to about 50% by weight of a particulate water-soluble adhesive material;

0% to about 20% by weight of a first fibrous component;

semihydrate of calcium sulfate;

an accelerator; and

a filler,

further characterized by absence of a retardant

wherein the particulate material comprises particles having a mean diameter of about 10 microns to about 100 microns, and is suitable for use in three dimensional printing to form an article comprised of a plurality of layers, the layers including a reaction product of the particulate material and a aqueous fluid that contacts the particulate material during three dimensional printing, the particulate material being capable of supporting the article during three dimensional printing and suitable for being spread in a layer of dry particles having a thickness selected from a range of about 12 to about 125 microns.

2. The three dimensional printing composition of claim 1, further comprising from about 0% to about 30% of a second fibrous component.

3. The three dimensional printing composition of claim 2, wherein the second fibrous component has a length of about 30 microns to about 100 microns.

4. The three dimensional printing composition of claim 2, wherein the second fibrous component has a length less than half the length of the first fibrous component.

5. The three dimensional printing composition of claim 1, further comprising about 0 to about 3 percent, by weight of the total composition, of a printing aid.

6. The three dimensional printing composition of claim 5, wherein the printing aid is selected from the group consisting of lecithin, hydrophilic lecithin, polypropylene glycol, citronellol, and combinations thereof.

7. The three dimensional printing composition of claim 1, wherein the particulate water-soluble adhesive material has an average particle grain size between about 10 and about 20 microns.

8. The three dimensional printing composition of claim 1, wherein the particulate water-soluble adhesive material is a polymer.

9. The three dimensional printing composition of claim 8, wherein the polymer is selected from the group consisting of polyethylene glycol, sodium polyacrylate, polyvinyl alcohol, polyvinyl pyrrolidone, sodium polyacrylate copolymer with maleic acid, polyvinyl pyrrolidone copolymer with vinyl acetate, and combinations thereof.

10. The three dimensional printing composition of claim 1, wherein the particulate water-soluble adhesive material is a carbohydrate.

11. The three dimensional printing composition of claim 1, wherein the filler comprises a carbohydrate.

12. The three dimensional printing composition of claim 10 or 11, wherein the carbohydrate is selected from the group consisting of acacia gum, locust bean gum, sodium carboxy methylcellulose, sodium alginate, hydroxypropyl cellulose, dextrin, maltodextrin, cellulose gel, starch, sugar, and combinations thereof.

13. The three dimensional printing composition of claim 10 or 11, wherein the carbohydrate is a starch selected from the group consisting of:

pregelatinized starch, acid-modified starch, and hydrolyzed starch.

14. The three dimensional printing composition of claim 10 or 11, wherein the carbohydrate is a sugar or a sugar alcohol selected from the group consisting of sucrose, dextrose, fructose, lactose, polydextrose, sorbitol, xylitol, and combinations thereof.

15. The three dimensional printing composition of claim 1, wherein the particulate water-soluble adhesive material is an organic acid.

16. The three dimensional printing composition of claim 1, wherein filler comprises an organic acid.

17. The three dimensional printing composition of claim 15 or 16, wherein the organic acid is selected from the group consisting of citric acid, succinic acid, polyacrylic acid, and combinations thereof.

18. The three dimensional printing composition of claim 1, wherein the particulate water-soluble adhesive material is an inorganic compound.

19. The three dimensional printing composition of claim 1, wherein the filler comprises an inorganic compound.

20. The three dimensional printing composition of claim 18 or 19, wherein the inorganic compound is selected from the group consisting of bentonite, sodium silicate, salt, and combinations thereof.

21. The three dimensional printing composition of claim 1, wherein the fibrous component has a length of about 60 microns to about 200 microns.

22. The three dimensional printing composition of claim 21, wherein the fibrous component is a polymeric fiber.

23. The three dimensional printing composition of claim 22, wherein the polymeric fiber is selected from the group consisting of:

cellulose fiber, cellulose derivative fiber, ceramic fiber, graphite fiber, and fiberglass.

24. The three dimensional printing composition of claim 21, wherein the fibrous component is selected from the group consisting of:

cellulose fiber, silicon carbide fiber, graphite fiber, aluminosilicate fiber, polypropylene fiber and fiberglass.

25. The three dimensional printing composition of claim 1, wherein the adhesive material is about 30 percent, by weight, of the composition.

26. The three dimensional printing composition of claim 1, wherein the filler is about 60 percent, by weight, of the composition.

27. The three dimensional printing composition of claim 1, wherein the first fibrous component is about 10 percent, by weight, of the composition.

28. The three dimensional printing composition of claim 1, wherein the filler comprises up to about 80% by weight of the particulate material.

29. The three dimensional printing composition of claim 1, wherein the filler comprises up to about 30% by weight of the composition.

30. The three dimensional printing composition of claim 1, wherein the filler comprises a material selected from the group consisting of starch, glass beads, and a polymer.

31. A three dimensional printing composition comprising:

a dry, loose, free-flowing particulate material including;

about 10% to about 50% by weight of an adhesive material;

0% to about 20% by weight of a first fibrous component;

semihydrate of calcium sulfate; and

0% to about 80% by weight of a filler,

wherein the adhesive material comprises a polyvinyl pyrrolidone copolymer with vinyl acetate, the adhesive material has an average particle grain size between about 10 and about 20 microns, the filler has a mean particle size between about 20 and about 200 microns, the particulate material comprises particles having a mean diameter of about 10 microns to about 100 microns, and is suitable for use in three dimensional printing to form an article comprised of a plurality of layers, the layers including a reaction product of the particulate material and a aqueous fluid that contacts the particulate material during three dimensional printing, the particulate material being capable of supporting the article during three dimensional printing and suitable for being spread in a layer of dry particles.

32. A method of three dimensional printing, comprising:

providing a first layer of a three dimensional printing composition including a dry, loose, free-flowing particulate material including about 10% to about 50% by weight of a particulate adhesive material, 0% to about 20% by weight of a first fibrous component, and a filler comprising plaster, the layer comprising dry particles and having a thickness selected from a range of about 12 to about 125 microns;

delivering an aqueous fluid to a portion of the first particulate material layer;

allowing the portion of the first particulate material layer to solidify;

providing a second layer of the three dimensional printing composition including the particulate material;

delivering the fluid to a portion of the second particulate material layer; and

allowing the portion of the second particulate material layer to solidify,

to form at least a portion of a solid article including a plurality of layers,

wherein the particulate material is capable of supporting the article during three dimensional printing.

33. A three dimensional printing composition, comprising:

a dry, loose, free-flowing particulate material having a mean particle size between about 10 microns and about 300 microns, comprising

plaster,

an at least partially water soluble particulate adhesive material, and

a printing aid,

wherein the particulate adhesive material is up to about 50 percent, by weight, of the composition, and the particulate material is suitable for use in three dimensional printing to form an article comprised of a plurality of layers, the layers including a reaction product of the particulate material and an aqueous fluid that contacts the particulate material during three dimensional printing, the particulate material being capable of supporting the article during three dimensional printing and suitable for being spread in a layer of dry particles having a thickness selected from a range of about 12 to about 125 microns.

34. The three dimensional printing composition of claim 33, further comprising a filler.

35. The three dimensional printing composition of claim 34, wherein the filler is a carbohydrate.

36. The three dimensional printing composition of claim 34, wherein the filler is a starch.

37. The three dimensional printing composition of claim 33, wherein the printing aid is selected from the group consisting of:

polyethylene glycol, sorbitan trioleate, sorbitan monooleate, ethlyene glycol di-octyl-decyl ester, ethoxylated fatty-acid esters of sorbitan, glycerol, ethylene glycol, propylene glycol, polypropylene glycol, citronellol, and combinations thereof.

38. The three dimensional printing composition of claim 33, wherein the at least partially water soluble adhesive is a starch.

39. The three dimensional printing composition of claim 38 or 36, wherein the starch is selected from the group consisting of:

pregelatinized starch, acid-modified starch, cationically modified starch, hydrolyzed starch, and combinations thereof.

40. The three dimensional printing composition of claim 38, further comprising a fiber.

41. The three dimensional printing composition of claim 40, wherein the fiber is selected from the group consisting of:

polymeric fiber, rayon fiber, ceramic fiber, graphite fiber, fiberglass, and combinations thereof.

42. The three dimensional printing composition of claim 41, wherein the polymeric fiber is a material selected from the group consisting of:

cellulose fiber, a polymer derived from an alkyl monomer, a polymer derived from an alkene monomer of up to 8 carbon atoms, and combinations thereof.

43. A three dimensional printing composition, comprising:

a dry, loose, free-flowing particulate material including;

semihydrate of calcium sulfate;

a first particulate adhesive that is partially hydrolyzed polyvinyl alcohol;

a second particulate adhesive; and

an accelerator,

further characterized by absence of a retardant,

wherein the particulate material comprises particles having a mean diameter of about 10 microns to about 100 microns, and is suitable for use in three dimensional printing to form an article comprised of a plurality of layers, the layers including a reaction product of the particulate material and an aqueous fluid that contacts the particulate material during three dimensional printing, the particulate material being capable of supporting the article during three dimensional printing and suitable for being spread in a layer having a thickness selected from a range of about 12 to about 125 microns.

44. The three dimensional printing composition of claim 43, further comprising a filler.

45. The three dimensional printing composition of claim 44, wherein the filler is selected from the group consisting of:

silica, limestone, starch, and combinations thereof.

46. The three dimensional printing composition of claim 43, wherein the accelerator is selected from the group consisting of:

terra alba, potassium sulfate, sodium chloride, undercalcined plaster, alum, potassium alum, lime, calcined lime, and combinations thereof.

47. The three dimensional printing composition of claim 43, wherein the second adhesive is Dextrin.

48. The three dimensional printing composition of claim 43, wherein the second adhesive is Cellulose gel.

49. The three dimensional printing composition of claim 43, wherein the composition includes less than about 20% of the accelerator by weight of the composition.

50. The three dimensional printing composition of claim 49, wherein the composition includes less than about 5% of the accelerator by weight of the composition.

51. The three dimensional printing composition of claim 50, wherein the composition includes less than about 1% of the accelerator by weight of the composition.

52. The three dimensional printing composition of claim 43, wherein the composition includes about 60 to about 80% of semihydrate of calcium sulfate, by weight of the composition.

53. The three dimensional printing composition of claim 52, wherein the composition includes about 15 to about 30% of the first adhesive, by weight of the composition.

54. The three dimensional printing composition of claim 53, wherein the composition includes about 2 to about 10% of the second adhesive, by weight of the composition.

55. A three dimensional printing composition comprising:

a dry, loose, free-flowing particulate material including;

semihydrate of calcium sulfate;

a first particulate adhesive;

a second particulate adhesive; and

an accelerator,

further characterized by absence of a retardant,

wherein the first adhesive is Dextrin and the particulate material comprises particles having a mean diameter of about 10 microns to about 100 microns, and is suitable for use in three dimensional printing to form an article comprised of a plurality of layers, the layers including a reaction product of the particulate material and an aqueous fluid that contacts the particulate material during three dimensional printing, the particulate material being capable of supporting the article during three dimensional printing and suitable for being spread in a layer of dry particles having a thickness selected from a range of about 12 microns to about 125 microns.

56. A kit for three dimensional printing, comprising:

a three dimensional printing composition; and

an aqueous fluid comprising an accelerator,

wherein the three dimensional printing composition comprises a dry, loose, free-flowing particulate material including plaster and a first particulate adhesive, the particulate material is suitable for use in three dimensional printing to form an article comprised of a plurality of layers, the layers including a reaction product of the particulate material and the aqueous fluid that contacts the particulate material during three dimensional printing, the particulate material being capable of supporting the article during three dimensional printing and suitable for being spread in a layer of dry particles having a thickness selected from a range of about 12 to about 125 microns.

57. The kit of claim 56, wherein the three dimensional printing composition further includes a second adhesive.

58. The kit of claim 57, wherein the three dimensional printing composition further comprises an accelerator.

59. A kit comprising:

a three dimensional printing composition; and

an aqueous fluid comprising a humectant,

wherein the three dimensional printing composition comprises a dry, loose, free-flowing particulate material including plaster and a first particulate adhesive, the particulate material is suitable for use in three dimensional printing to form an article comprised of a plurality of layers, the layers including a reaction product of the particulate material and the aqueous fluid that contacts the particulate material during three dimensional printing, the particulate material being capable of supporting the article during three dimensional printing and suitable for being spread in a layer of dry particles having a thickness selected from a range of about 12 to about 125 microns.

60. A kit comprising:

a three dimensional printing composition; and

an aqueous fluid comprising a flow rate enhancer,

wherein the three dimensional printing composition comprises a dry, loose, free-flowing particulate material including plaster and a first particulate adhesive, the particulate material is suitable for use in three dimensional printing to form an article comprised of a plurality of layers, the layers including a reaction product of the particulate material and the aqueous fluid that contacts the particulate material during three dimensional printing, the particulate material being capable of supporting the article during three dimensional printing and suitable for being spread in a layer of dry particles having a thickness selected from a range of about 12 to about 125 microns.

61. A three dimensional printing composition, comprising:

a dry, loose, free-flowing particulate material including;

plaster,

a particulate adhesive,

an accelerator,

a filler, and

an oil,

wherein the particulate material is suitable for use in three dimensional printing to form an article comprised of a plurality of layers, the layers including a reaction product of the particulate material and an aqueous fluid that contacts the particulate material during three dimensional printing.

62. The three dimensional printing composition of claim 61, wherein the filler is selected from the group consisting of:

silica, limestone, starch, glass beads, sand, rayon fiber, cellulose, limestone, zircon, olivine, staurolite, chromite, alumina, mullite, bohemite, kaolin, bentonite, and combinations thereof.

63. The three dimensional printing composition of claim 61, wherein the accelerator is selected from the group consisting of:

terra alba, undercalcined plaster, alum, potassium alum, lime, calcined lime, barium sulfate, magnesium sulfate, zinc sulfate, calcium chloride, potassium sulfate, sodium sulfate, ammonium sulfate, calcium formate, calcium nitrate, sodium silicate, potassium chloride, sodium chloride, animonium chloride, and combinations thereof.

64. The three dimensional printing composition of claim 61, wherein the oil is selected from the group consisting of:

oleoyl alcohol, dodecyl alcohol, other aliphatic alcohols, polypropylene glycol, polyethylene glycol, ethers of polyethylene glycol, ethers of polypropylene glycol, mineral oil, fatty esters selected from the group consisting of methyl oleate and ethylene glycol octyl/decyl ester; and

glycerol tributyrate.