Three dimensional printing material system and method

• US 20040056378A1
• Filed: 09/25/2002
• Published: 03/25/2004
• Est. Priority Date: 09/25/2002
• Status: Active Grant

• Current Assignee: 3D Systems, Inc. (3D Systems Corporation)
• Original Assignee: Z CORPORATION (A Holdings Corp.)
• Inventors: Bredt, James F., Gilchrist, Grieta, Clark, Sarah
• Granted Patent: US 7,087,109 B2
• Time in Patent Office: Days
• US Class Current: 264/109
• 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 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 70/10 Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
• CPC Class Codes: B33Y 80/00 Products made by additive manufacturing
• CPC Class Codes: C04B 14/02 Granular materials , e.g. microballoons
• CPC Class Codes: C04B 14/30 Oxides other than silica ferrites C04B14/363
• CPC Class Codes: C04B 2103/0092 for improving green strength
• CPC Class Codes: C04B 2103/10 Accelerators; Activators
• CPC Class Codes: C04B 2111/00181 Mixtures specially adapted for three-dimensional printing (3DP), stereo-lithography or prototyping
• CPC Class Codes: C04B 22/064 of the alkaline-earth metals
• CPC Class Codes: C04B 24/122 Hydroxy amines
• CPC Class Codes: C04B 28/14 containing calcium sulfate cements gypsum-paper plates E04C
• CPC Class Codes: C04B 28/30 containing magnesium cements or similar cementsmagnesium oxide cements C04B28/10
• CPC Class Codes: C04B 28/34 containing cold phosphate binders

Abstract

The present invention is directed to a three-dimensional printing system and method, and an article made therefrom. The method of the present invention includes building cross-sectional portions of a three dimensional article, and assembling the individual cross-sectional areas in a layer-wise fashion to form a final article. The individual cross-sectional areas are built using an ink-jet printhead to deliver an aqueous fluid to a particle material that includes a first particulate material, a second particulate material, and a third particulate material, wherein the first and second particulate materials react in the presence of the fluid in a period of time, and the third particulate material reacts in the presence of the fluid to form a solid in a longer period of time.

Claims

1. An article comprising:

a product of a mixture of a plurality of particles of;

a first particulate material;

a second particulate material; and

a third particulate material,

wherein the first particulate material and the second particulate material can react to form a solid in a period of time, and the third particulate material can solidify in a longer period of time.

2. The article of claim 1, wherein the first particulate material and the second particulate material react in the presence of a fluid.

3. The article of claim 2, wherein at least one of the first particulate material and the second particulate material is substantially soluble in the fluid.

4. The article of claim 1, wherein the first particulate material is a phosphate.

5. The article of claim 4, wherein the phosphate is selected from the group consisting of monoammonium phosphate;

sodium aluminum phosphate, acidic;

monocalcium phosphate, anhydrous;

monopotassium phosphate;

monosodium phosphate; and

aluminum acid phosphate.

6. The article of claim 4, wherein the phosphate is selected from the group consisting of:

sodium tripolyphosphate;

sodium hexametaphosphate;

phosphoric acid, sodium salt;

sodium trimetaphosphate; and

ammonium polyphosphate.

7. The article of claim 4, wherein the phosphate is selected from the group consisting of diammonium phosphate;

dipotassium phosphate;

disodium phosphate;

monocalcium phosphate dihydrate;

monocalcium phosphate, monohydrate;

dicalcium phosphate, dihydrate;

dicalcium phosphate, anhydrous;

tricalcium phosphate;

disodium phosphate; and

tripotassium phosphate.

8. The article of claim 4, wherein the phosphate is selected from the group consisting of sodium acid pyrophosphate;

tetrasodium pyrophosphate;

tetrapotassium pyrophosphate.

9. The article of claim 4, wherein the phosphate is selected from the group consisting of:

monocalcium phosphate anhydrous;

acidic sodium aluminum phosphate;

acidic aluminum phosphate;

monoammonium phosphate;

monopotassium phosphate;

monosodium phosphate; and

combinations thereof.

10. The article of claim 1, wherein the second particulate material is an alkaline oxide, alkaline hydroxide, or combination thereof.

11. The article of claim 10, wherein the alkaline oxide is selected from the group consisting of:

zinc oxide;

magnesium oxide;

calcium oxide;

copper oxide;

beryllium oxide;

bismuth oxide;

cadmium oxide;

tin oxide;

red lead oxide; and

combinations thereof.

12. The article of claim 10, wherein the alkaline hydroxide is selected from the group consisting of:

magnesium hydroxide;

cobalt trihydroxide;

beryllium dihydroxide and combinations thereof.

13. The article of claim 10, wherein the alkaline oxide is magnesium oxide.

14. The article of claim 10, wherein the first particulate material is selected from the group consisting of:

polyacrylic acid, polymethacrylic acid, citric acid, succinic acid, malic acid, copolymers of polyacrylic acid and methacrylic acid with maleic acid, and alkali salts thereof.

15. The article of claim 1, wherein the third particulate material is an adhesive.

16. The article of claim 15, wherein the adhesive is selected from the group consisting of:

copolymer of octylacrylamide/acrylates/butylaminoethyl methacrylate;

polyvinyl alcohol;

polyethylene oxide;

sodium polystyrene sulfonate;

polyacrylic acid;

polyvinyl pyrrolidone;

maltodextrine;

hydrolyzed gelatin;

sugar;

hydrolyzed starch;

sodium salt of polymethacrylic acid;

ammonium salt of polymethacrylic acid;

polyvinyl sulfonic acid;

sulfonated polyester;

poly(2-ethyl-2-oxazoline);

polymethacrylic acid;

sodium salt of polyacrylic acid;

ammonium salt of polyacrylic acid; and

combinations thereof.

17. The article of claim 1, wherein the mixture of plurality of particles further comprises a filler.

18. The article of claim 17, wherein the filler is selected from the group consisting of:

limestone, staurolite, silica sand, zircon sand, olivine sand, chromite sand, magnesite, alumina silicate, calcium silicate, fused silica, calcium phosphate, rutile, bentonite, montmorillonite, glass, chamotte, fireclay, and mixtures thereof.

19. The article of claim 2, wherein the fluid is aqueous.

20. The article of claim 1, wherein the first particulate material is plaster.

21. The article of claim 20, wherein the second particulate material is an accelerator.

22. The article of claim 21, wherein the accelerator is selected from the group consisting of Terra Alba;

potassium sulfate;

barium sulfate;

ammonium sulfate;

sodium chloride;

under-calcined plaster;

alum;

potassium alum;

lime;

calcined clay; and

combinations thereof.

23. The article of claim 22, wherein the third particulate material is an adhesive.

24. The article of claim 23, wherein the adhesive is selected from the group consisting of:

copolymer of octlacrylamide/acrylates/butylaminoethyl methacrylate;

polyvinyl alcohol;

polyethylene oxide;

sodium polystyrene sulfonate;

polyacrylic acid;

polyvinyl pyrrolidone;

maltodextrine;

hydrolyzed gelatin;

sugar;

hydrolyzed starch;

sodium salt of polymethacrylic acid;

ammonium salt of polymethacrylic acid;

polyvinyl sulfonic acid;

sulfonated polyester;

poly(2-ethyl-2-oxazoline);

polymethacrylic acid;

sodium salt of polyacrylic acid;

ammonium salt of polyacrylic acid; and

combinations thereof.

25. The article of claim 1, wherein the first particulate material is selected from the group consisting of:

a sulfate containing compound;

a chloride containing compound; and

combinations thereof.

26. The article of claim 25, wherein the sulfate containing compound is selected from the group consisting of:

magnesium sulfate, zinc sulfate, and combinations thereof.

27. The article of claim 25, wherein the chloride containing compound is selected from the group consisting of:

magnesium chloride, zinc chloride, calcium chloride, and combinations thereof.

28. A compound used in three dimensional printing comprising:

a first particulate material;

a second particulate material; and

a third particulate material,

wherein the first particulate material and the second particulate material can react to form a solid in a period of time, and the third particulate material can solidify in a longer period of time.

29. The compound of claim 28, wherein the first particulate material and the second particulate material react in the presence of a fluid.

30. The compound of claim 29, wherein at least one of the first particulate material and the second particulate material is substantially soluble in the fluid.

31. The compound of claim 28, wherein the first particulate material is a phosphate.

32. The compound of claim 31, wherein the phosphate is selected from the group consisting of monoammonium phosphate;

sodium aluminum phosphate, acidic;

monocalcium phosphate, anhydrous;

monopotassium phosphate;

monosodium phosphate; and

aluminum acid phosphate.

33. The compound of claim 31, wherein the phosphate is selected from the group consisting of:

sodium tripolyphosphate;

sodium hexametaphosphate;

phosphoric acid, sodium salt;

sodium trimetaphosphate; and

ammonium polyphosphate.

34. The compound of claim 31, wherein the phosphate is selected from the group consisting of diammonium phosphate;

dipotassium phosphate;

disodium phosphate;

monocalcium phosphate dihydrate;

monocalcium phosphate, monohydrate;

dicalcium phosphate, dihydrate;

dicalcium phosphate, anhydrous;

tricalcium phosphate;

disodium phosphate; and

tripotassium phosphate.

35. The compound of claim 31, wherein the phosphate is selected from the group consisting of sodium acid pyrophosphate;

tetrasodium pyrophosphate;

tetrapotassium pyrophosphate.

36. The compound of claim 31, wherein the phosphate is selected from the group consisting of:

monocalcium phosphate anhydrous;

acidic sodium aluminum phosphate;

acidic aluminum phosphate;

monoammonium phosphate;

monopotassium phosphate;

monosodium phosphate; and

combinations thereof.

37. The compound of claim 28, wherein the second particulate material is an alkaline oxide, alkaline hydroxide, or combination thereof.

38. The compound of claim 37, wherein the alkaline oxide is selected from the group consisting of:

zinc oxide;

magnesium oxide;

calcium oxide;

copper oxide;

beryllium oxide;

bismuth oxide;

cadmium oxide;

tin oxide;

red lead oxide; and

combinations thereof.

39. The compound of claim 37, wherein the alkaline hydroxide is selected from the group consisting of:

magnesium hydroxide;

cobalt trihydroxide;

beryllium dihydroxide and combinations thereof.

40. The compound of claim 37, wherein the alkaline oxide is magnesium oxide.

41. The compound of claim 37, wherein the first particulate material is selected from the group consisting of:

polyacrylic acid, polymethacrylic acid, citric acid, succinic acid, malic acid, copolymers of polyacrylic acid and methacrylic acid with maleic acid, and alkali salts thereof.

42. The compound of claim 28, wherein the third particulate material is an adhesive.

43. The compound of claim 42, wherein the adhesive is selected from the group consisting of:

copolymer of octylacrylamide/acrylates/butylaminoethyl methacrylate;

polyvinyl alcohol;

polyethylene oxide;

sodium polystyrene sulfonate;

polyacrylic acid;

polyvinyl pyrrolidone;

maltodextrine;

hydrolyzed gelatin;

sugar;

hydrolyzed starch;

sodium salt of polymethacrylic acid;

ammonium salt of polymethacrylic acid;

polyvinyl sulfonic acid;

sulfonated polyester;

poly(2-ethyl-2-oxazoline);

polymethacrylic acid;

sodium salt of polyacrylic acid;

aminonium salt of polyacrylic acid; and

combinations thereof.

44. The compound of claim 28, wherein the mixture of plurality of particles further comprises a filler.

45. The compound of claim 44, wherein the filler is selected from the group consisting of:

limestone, staurolite, silica sand, zircon sand, olivine sand, chromite sand, magnesite, alumina silicate, calcium silicate, fused silica, calcium phosphate, rutile, bentonite, montmorillonite, glass, chamotte, fireclay, and mixtures thereof.

46. The compound of claim 29, wherein the fluid is aqueous.

47. The compound of claim 28, wherein the first particulate material is plaster.

48. The compound of claim 47, wherein the second particulate material is an accelerator.

49. The compound of claim 48, wherein the accelerator is selected from the group consisting of Terra Alba;

potassium sulfate;

barium sulfate;

ammonium sulfate;

sodium chloride;

under-calcined plaster;

alum;

potassium alum;

lime;

calcined clay; and

combinations thereof.

50. The compound of claim 49, wherein the third particulate material is an adhesive.

51. The compound of claim 50, wherein the adhesive is selected from the group consisting of:

copolymer of octlacrylamide/acrylates/butylaminoethyl methacrylate;

polyvinyl alcohol;

polyethylene oxide;

sodium polystyrene sulfonate;

polyacrylic acid;

polyvinyl pyrrolidone;

maltodextrine;

hydrolyzed gelatin;

sugar;

hydrolyzed starch;

sodium salt of polymethacrylic acid;

ammonium salt of polymethacrylic acid;

polyvinyl sulfonic acid;

sulfonated polyester;

poly(2-ethyl-2-oxazoline);

polymethacrylic acid;

sodium salt of polyacrylic acid;

ammonium salt of polyacrylic acid; and

combinations thereof.

52. The compound of claim 28, wherein the first particulate material is selected from the group consisting of:

a sulfate containing compound, a chloride containing compound; and

combinations thereof.

53. The compound of claim 52, wherein the sulfate containing compound is selected from the group consisting of:

magnesium sulfate, zinc sulfate, and combinations thereof.

54. The compound of claim 52, wherein the chloride containing compound is selected from the group consisting of:

magnesium chloride, zinc chloride, calcium chloride, and combinations thereof.

55. A method of three-dimensional printing, comprising:

providing a layer of a dry particulate material comprising a first particulate material, a second particulate material, and a third particulate material;

dispensing a fluid onto a region of the first layer;

causing a reaction between the first and second particulate materials to occur, the reaction causing a solidified material to form in the region; and

causing the third particulate material to solidify in the region, wherein the reaction between the first and second particulate materials occurs in a period of time, and the third particulate material solidifies in a longer period of time.

56. The method of claim 55, further comprising:

providing a second layer of the dry particulate material;

dispensing the fluid onto a region of the second layer;

causing a reaction between the first and second particulate materials to occur, the reaction causing a solidified material to form in the region of the second layer and at least a portion of the region of the first layer;

causing the third particulate material to solidify in the region of the second layer and at least a portion of the region of the first layer.

57. The method of claim 55, wherein the fluid is aqueous.

58. The method of claim 57, wherein the fluid comprises an amino alcohol.

59. The method of claim 58, wherein the amino alcohol is selected from the group consisting of:

2-amino-2-methyl-1-propanol;

1-amino-2-propanol;

2-dimethylamino-2-methyl-1-propanol;

N,N-diethylethanolamine;

N-methyldiethanolamine;

N,N-dimethylethanolamine;

triethanolamine;

2-aminoethanol;

1-[bis[3-(dimethylamino)propyl]amino]-2-propanol;

3-amino-1-propanol;

2-(2-aminoethylamino)ethanol;

tris(hydroxymethyl)aminomethane;

2-amino-2-ethyl-1,3-propanediol;

2-amino-2-methyl-1,3-propanediol;

diethanolamine;

1,3-bis(dimethylamino)-2-propanol; and

combinations thereof

60. The method of claim 55, wherein at least one of the first particulate material and the second particulate material is substantially soluble in the fluid.

61. The method of claim 55, wherein the first particulate material is a phosphate.

62. The method of claim 61, wherein the phosphate is selected from the group consisting of monoammonium phosphate;

sodium aluminum phosphate, acidic;

monocalcium phosphate, anhydrous;

monopotassium phosphate;

monosodium phosphate; and

aluminum acid phosphate.

63. The method of claim 61, wherein the phosphate is selected from the group consisting of:

sodium tripolyphosphate;

sodium hexametaphosphate;

phosphoric acid, sodium salt;

sodium trimetaphosphate; and

ammonium polyphosphate.

64. The method of claim 61, wherein the phosphate is selected from the group consisting of diammonium phosphate;

dipotassium phosphate;

disodium phosphate;

monocalcium phosphate dihydrate;

monocalcium phosphate, monohydrate;

dicalcium phosphate, dihydrate;

dicalcium phosphate, anhydrous;

tricalcium phosphate;

disodium phosphate; and

tripotassium phosphate.

65. The method of claim 61, wherein the phosphate is selected from the group consisting of sodium acid pyrophosphate;

tetrasodium pyrophosphate;

tetrapotassium pyrophosphate.

66. The method of claim 61, wherein the phosphate is selected from the group consisting of:

monocalcium phosphate anhydrous;

acidic sodium aluminum phosphate;

acidic aluminum phosphate;

monoammonium phosphate;

monopotassium phosphate;

monosodium phosphate; and

combinations thereof.

67. The method of claim 55, wherein the second particulate material is an alkaline oxide, alkaline hydroxide, or combination thereof.

68. The method of claim 67, wherein the alkaline oxide is selected from the group consisting of:

zinc oxide;

magnesium oxide;

calcium oxide;

copper oxide;

beryllium oxide;

bismuth oxide;

cadmium oxide;

tin oxide;

red lead oxide; and

combinations thereof.

69. The method of claim 67, wherein the alkaline hydroxide is selected from the group consisting of:

magnesium hydroxide;

cobalt trihydroxide;

beryllium dihydroxide and combinations thereof.

70. The method of claim 67, wherein the alkaline oxide is magnesium oxide.

71. The method of claim 67, wherein the first particulate material is selected from the group consisting of:

polyacrylic acid, polymethacrylic acid, citric acid, succinic acid, malic acid, copolymers of polyacrylic acid and methacrylic acid with maleic acid, and alkali salts thereof.

72. The method of claim 55, wherein the third particulate material is an adhesive.

73. The method of claim 72, wherein the adhesive is selected from the group consisting of:

copolymer of octylacrylamide/acrylates/butylaminoethyl methacrylate;

polyvinyl alcohol;

polyethylene oxide;

sodium polystyrene sulfonate;

polyacrylic acid;

polyvinyl pyrrolidone;

maltodextrine;

hydrolyzed gelatin;

sugar;

hydrolyzed starch;

sodium salt of polymethacrylic acid;

ammonium salt of polymethacrylic acid;

polyvinyl sulfonic acid;

sulfonated polyester;

poly(2-ethyl-2-oxazoline);

polymethacrylic acid;

sodium salt of polyacrylic acid;

ammonium salt of polyacrylic acid; and

combinations thereof.

74. The method of claim 55, wherein the mixture of plurality of particles further comprises a filler.

75. The method of claim 74, wherein the filler is selected from the group consisting of:

limestone;

staurolite, silica sand, zircon sand, olivine sand, chromite sand, magnesite, alumina silicate, calcium silicate, fused silica, calcium phosphate, rutile, bentonite, montmorillonite, glass, chamotte, fireclay, and mixtures thereof.

76. The method of claim 55, wherein the first particulate material is plaster.

77. The method of claim 76, wherein the second particulate material is an accelerator.

78. The method of claim 77, wherein the accelerator is selected from the group consisting of Terra Alba;

potassium sulfate;

barium sulfate;

ammonium sulfate;

sodium chloride;

under-calcined plaster;

alum;

potassium alum;

lime;

calcined clay; and

combinations thereof.

79. The method of claim 78, wherein the third particulate material is an adhesive.

80. The method of claim 79, wherein the adhesive is selected from the group consisting of:

copolymer of octlacrylamide/acrylates/butylaminoethyl methacrylate;

polyvinyl alcohol;

polyethylene oxide;

sodium polystyrene sulfonate;

polyacrylic acid;

polyvinyl pyrrolidone;

maltodextrine;

hydrolyzed gelatin;

sugar;

hydrolyzed starch;

sodium salt of polymethacrylic acid;

ammonium salt of polymethacrylic acid;

polyvinyl sulfonic acid;

sulfonated polyester;

poly(2-ethyl-2-oxazoline);

polymethacrylic acid;

sodium salt of polyacrylic acid;

ammonium salt of polyacrylic acid; and

combinations thereof.

81. The method of claim 55, wherein t he first particulate material is selected from the group consisting of:

a sulfate containing compound;

a chloride contianing compound; and

combinations thereof.

82. The method of claim 81, wherein the sulfate containing compound is selected from the group consisting of:

magnesium sulfate, zinc sulfate, and combinations thereof.

83. The method of claim 81, wherein the chloride containing compound is selected from the group consisting of:

magnesium chloride, zinc chloride, calcium chloride, and combinations thereof.

84. A mixture of solids used in three dimensional printing that, when contacted by a fluid, undergoes a first solidification reaction beginning with the fluid contact and occurring at a first rate, and also undergoes a second solidification reaction beginning with the fluid contact and occurring at a second rate slower than the first rate.