Three dimensional printing material system and method

• US 20060230984A1
• Filed: 06/15/2006
• Published: 10/19/2006
• Est. Priority Date: 09/25/2002
• Status: Abandoned Application

• Current Assignee: Z CORPORATION (A Holdings Corp.)
• Original Assignee: Z CORPORATION (A Holdings Corp.)
• Inventors: Gilchrist, Grieta, Bredt, James F., Clark, Sarah L.
• Application Number:
  US11/453,695
• Publication Number:
  US 20060230984A1
• Time in Patent Office: Days
• US Class Current: 106/690
• 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. A solid article comprising:

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

a first particulate material comprising a phosphate;

a second particulate material comprising an oxide; and

a third particulate material comprising an adhesive,

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 when the mixture is contacted by a fluid during three-dimensional printing, the article having been formed by three-dimensional printing and comprising a plurality of layers of the mixture.

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.

5. The article of claim 1, 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 1, wherein the phosphate is selected from the group consisting of:

sodium tripolyphosphate;

sodium hexametaphosphate;

sodium polyphosphate, anhydrous;

phosphoric acid, sodium salt;

sodium trimetaphosphate; and

ammonium polyphosphate.

7. The article of claim 1, 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 1, wherein the phosphate is selected from the group consisting of sodium acid pyrophosphate;

tetrasodium pyrophosphate; and

tetrapotassium pyrophosphate.

10. The article of claim 1, wherein the second particulate material comprises at least one of an alkaline oxide, an alkaline hydroxide, and a 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;

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 comprises magnesium oxide.

16. The article of claim 1, 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.

4. (canceled)

9. (canceled)

14-15. -15. (canceled)

20-27. -27. (canceled)

28. A compound used in three dimensional printing comprising:

a dry particulate mixture of;

a first particulate material comprising a phosphate;

a second particulate material comprising an oxide; and

a third particulate material comprising an adhesive,

wherein the dry particulate mixture can be used in three-dimensional printing to form an article comprised of a plurality of layers, 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 when the mixture is contacted by a fluid during three-dimensional printing.

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

32. The compound of claim 28, 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 28, wherein the phosphate is selected from the group consisting of:

sodium tripolyphosphate;

sodium hexametaphosphate;

sodium polyphosphate, anhydrous;

phosphoric acid, sodium salt;

sodium trimetaphosphate; and

ammonium polyphosphate.

34. The compound of claim 28, 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 28, wherein the phosphate is selected from the group consisting of sodium acid pyrophosphate;

tetrasodium pyrophosphate; and

tetrapotassium pyrophosphate.

37. The compound of claim 28, wherein the second particulate material comprises at least one of an alkaline oxide, an alkaline hydroxide, and a 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;

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 comprises magnesium oxide.

43. The compound of claim 28, 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.

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.

31. (canceled)

36. (canceled)

41-42. -42. (canceled)

47-83. -83. (canceled)

84. A dry particulate mixture of solids used for three dimensional printing that, when contacted by a fluid during three-dimensional printing to form an article composed of a plurality of layers, 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, wherein the dry particulate mixture comprises:

a first particulate material comprising a phosphate;

a second particulate material comprising an oxide; and

a third particulate material comprising an adhesive.

85. The compound of claim 84, 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.

86. The compound of claim 84, wherein the phosphate is selected from the group consisting of:

sodium tripolyphosphate;

sodium hexametaphosphate;

sodium polyphosphate, anhydrous;

phosphoric acid, sodium salt;

sodium trimetaphosphate; and

ammonium polyphosphate.

87. The compound of claim 84, 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.

88. The compound of claim 84, wherein the phosphate is selected from the group consisting of sodium acid pyrophosphate;

tetrasodium pyrophosphate; and

tetrapotassium pyrophosphate.

89. The compound of claim 84, wherein the second particulate material comprises at least one of an alkaline oxide, an alkaline hydroxide, and a combination thereof.

90. The compound of claim 89, wherein the alkaline oxide is selected from the group consisting of:

zinc oxide;

magnesium oxide;

calcium oxide;

copper oxide;

bismuth oxide;

cadmium oxide;

tin oxide;

red lead oxide; and

combinations thereof.

91. The compound of claim 89, wherein the alkaline hydroxide is selected from the group consisting of:

magnesium hydroxide;

cobalt trihydroxide;

beryllium dihydroxide and combinations thereof.

92. The compound of claim 89, wherein the alkaline oxide comprises magnesium oxide.

93. The compound of claim 84, 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.