Three dimensional printing materials system

• US 6,416,850 B1
• Filed: 01/29/1999
• Issued: 07/09/2002
• 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: Bredt, James F., Russell, David B., Anderson, Timothy C.
• Primary Examiner(s): Morris, Terrell
• Assistant Examiner(s): ROCHE, LEANNA M
• Application Number:
  US09/240,252
• Time in Patent Office: 1,257 Days
• Field of Search: 428/297.4, 428/300.4, 106/499, 106/206.1
• US Class Current: 428/297.4
• 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 40/20 Post-treatment, e.g. curing, coating or polishing
• 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: C04B 12/04 Alkali metal or ammonium silicate cements ; Alkyl silicate cements; Silica sol cements; Soluble silicate cements alkali metal silicates per se, their preparation C01B33/32; ammonium silicates per se, their preparation C01C1/00
• CPC Class Codes: C04B 14/104 Bentonite, e.g. montmorillonite
• CPC Class Codes: C04B 14/386 Carbon carbon nanotubes C04B14/026
• CPC Class Codes: C04B 14/42 Glass
• CPC Class Codes: C04B 14/46 Rock wool ; Ceramic or silicate fibres C04B14/40, C04B14/42 take precedence
• CPC Class Codes: C04B 18/24 Vegetable refuse, e.g. rice husks, maize-ear refuse; Cellulosic materials, e.g. paper , cork
• CPC Class Codes: C04B 2103/54 Pigments; Dyes
• CPC Class Codes: C04B 2111/00181 : Mixtures specially adapted for three-dimensional printing (3DP), stereo-lithography or prototyping
• CPC Class Codes: C04B 22/143 : Calcium-sulfate
• CPC Class Codes: C04B 24/02 : Alcohols; Phenols; Ethers
• CPC Class Codes: C04B 24/38 : Polysaccharides or derivatives thereof C04B24/243 takes precedence
• CPC Class Codes: C04B 26/02 : Macromolecular compounds
• CPC Class Codes: C04B 26/06 : Acrylates
• CPC Class Codes: C04B 26/28 : Polysaccharides or derivatives thereof
• CPC Class Codes: C04B 28/001 : containing unburned clay polymer binder - clay mixtures used in well cementing C09K8/44
• CPC Class Codes: C04B 28/14 : containing calcium sulfate cements gypsum-paper plates E04C
• CPC Class Codes: C04B 28/26 : Silicates of the alkali metals
• 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
• CPC Class Codes: Y02W 30/91 : Use of waste materials as fillers for mortars or concrete
• CPC Class Codes: Y10T 428/24994 : Fiber embedded in or on the surface of a polymeric matrix
• CPC Class Codes: Y10T 428/249949 : Two or more chemically different fibers

Abstract

The present invention is directed to a Three Dimensional Printing materials systems and method that satisfies the need for a quick, reliable, safe, and inexpensive method for producing both appearance models and small numbers of functional parts in an office environment. 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 by using an ink-jet printhead to deliver an aqueous solvent to an adhesive particulate mixture, causing the particles of the mixture to adhere together, and to previous cross-sectional areas.

Claims

1. An article, comprising;

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

an adhesive; and

a filler;

wherein said mixture of a plurality of particles further comprises a first fibrous component and a fluid that activates said adhesive to form an essentially solid article composed of said plurality of particles;

said adhesive substantially soluble in, and said filler sparingly soluble in, said fluid;

the article further comprising adjacent layers, each layer comprising the product of the mixture of particles and having a contour with an edge, and a final shape of the article being defined by the edge of each of the layers, wherein either a portion of the edge of a first layer is offset from a portion of the edge of an adjacent layer to form an article having an undercut and/or overhang, or a continuous first layer is provided with a discontinuous adjacent layer to form an article having a cavity.

2. The article of claim 1, wherein said mixture comprises a second fibrous component.

3. The article of claim 2, wherein said first fibrous component has a mean length of about 60 microns to about 200 microns.

4. The article of claim 3, wherein said second fibrous component has a mean length of about 30 μ

m to about 100 μ

m.

5. The article of claim 4, wherein said first fibrous component and said second fibrous component are selected from the group consisting of polymeric fiber, ceramic fiber, graphite fiber and fiberglass.

6. The article of claim 5, wherein said first fibrous component and said second fibrous component are a polymeric fiber selected from the group consisting of cellulose and cellulose derivatives and substituted or unsubstituted, straight or branched, alkyl or alkene, monomers containing up to eight carbon atoms.

7. The article of claim 1, wherein said filler is an organic compound.

8. The article of claim 7, wherein said filler is an organic compound selected from the group consisting of sugars, sugar alcohols, organic acids and urea.

9. The article of claim 7, wherein said filler is a carbohydrate.

10. The article of claim 9, wherein said filler is a carbohydrate selected from the group comprising acacia gum, locust bean gum, pregelatinized starch, acid-modified starch, hydrolyzed starch, sodium carboxymethylcellulose, sodium alginate, hydroxypropyl cellulose, and hydrolyzed starch.

11. The article of claim 9, wherein said filler is maltodextrin.

12. The article of claim 11, wherein said filler is maltodextrin having a dextrose equivalent of 10.

13. The article of claim 1, wherein said filler is a polymer.

14. The article of claim 13, wherein said filler is a polymer selected from the group consisting of polyethylene glycol, sodium polyacrylate, polyvinyl alcohol, polyvinyl pyrrolidone, sodium polyacrylate copolymer with maleic acid, and polyvinyl pyrrolidone copolymer with vinyl acetate.

15. The article of claim 1, wherein said filler is a protein.

16. The article of claim 15, wherein said filler is a protein selected from the group consisting of gelatin, rabbit-skin glue and soy protein.

17. The article of claim 1, wherein said filler is an inorganic compound.

18. The article of claim 17, wherein said filler is an inorganic compound selected from the group consisting of sodium silicate, plaster, bentonite and salt.

19. The article of claim 1, wherein said adhesive is a water-soluble polymer.

20. The article of claim 19, wherein said adhesive is a water-soluble polymer selected from the group consisting of polyethylene glycol, sodium polyacrylate, polyvinyl alcohol, polyvinyl pyrrolidone, sodium polyacrylate copolymer with maleic acid, and polyvinyl pyrrolidone copolymer with vinyl acetate.

21. The article of claim 19, wherein said adhesive is a water soluble polymer that is a carbohydrate.

22. The article of claim 21, wherein said adhesive is a water soluble polymer that is a carbohydrate selected from the group comprising acacia gum, locust bean gum, pregelatinized starch, acid-modified starch, hydrolyzed starch, sodium carboxymethylcellulose, sodium alginate, hydroxypropyl cellulose, and hydrolyzed starch.

23. The article of claim 1, wherein said adhesive is an organic compound.

24. The article of claim 23, wherein said adhesive is an organic compound selected from the group consisting of sugars, sugar alcohols, organic acids and urea.

25. The article of claim 1, wherein said adhesive is a protein.

26. The article of claim 25, wherein said adhesive is a protein selected from the group consisting of gelatin, rabbit-skin glue and soy protein.

27. The article of claim 1, wherein said adhesive is an inorganic compound.

28. The article of claim 27, wherein said adhesive is an inorganic compound selected from the group consisting of sodium silicate, plaster, bentonite and salt.

29. The article of claim 1, wherein said fluid is added in an amount effective to form a solution of said adhesive.

30. The article of claim 29, wherein said fluid further comprises a humectant.

31. The article of claim 30, wherein said fluid further comprises a humectant selected from the group consisting of a polyhydric alcohol and urea.

32. The article of claim 31, wherein said fluid further comprises a flowrate enhancer.

33. The article of claim 29, wherein said fluid is a non-aqueous fluid.

34. The article of claim 33, wherein said fluid is a non-aqueous fluid selected from the group consisting of methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone, methylene chloride, acetic acid and ethyl acetoacetate.

35. The article of claim 1, further comprising a printing aid to reduce distortion in activated material.

36. The article of claim 1, wherein said fluid is an aqueous fluid.

37. The article of claim 1, wherein said mixture of said plurality of particles comprises:

adhesive in an amount of from about 10 to about 50 percent, by weight, of the total weight of the mixture;

filler in an amount of from about 0 to about 80 percent, by weight, of the total weight of the mixture;

fiber in an amount of from about 0 to about 30 percent, by weight, of the total weight of the mixture; and

said fluid comprises a humectant, in an amount of about 0-20 percent, by volume, based on the total volume of said fluid, a flowrate enhancer in an amount of about 0-10 percent, by volume, based on the total volume of said fluid; and

dye in an amount of about 0-0.1 percent, by volume, based on the total volume of said fluid.

38. The article of claim 37, wherein said mixture comprises a second fibrous component in an amount of about 10 percent, by weight, of the total mixture.

39. The article of claim 37, wherein said mixture of said plurality of particles comprises:

adhesive in an amount of about 30 percent, by weight, of the total weight of the mixture;

filler in an amount of from 60 percent, by weight, of the total weight of the mixture;

fiber in an amount of about 10 percent, by weight, of the total weight of the mixture; and

said fluid comprises said humectant, in an amount of about 5 percent, by volume, based on the total volume of said fluid, a flowrate enhancer in an amount of about 2 percent, by volume, based on the total volume of said fluid, and dye in an amount of from about 0-0.1 percent, by volume, based on the total volume of said fluid.

40. The article of claim 39, wherein said mixture comprises a second fibrous component in an amount of about 10 percent, by weight, of the total mixture.

41. The article of claim 1, wherein said particles each comprise said filler coated with said adhesive, said mixture self-adhering when activated by said fluid.

42. The article of claim 1, wherein said mixture comprises a first and second polymeric fibrous component.

43. The article of claim 42, wherein said filler is a water-soluble polymer.

44. The article of claim 43, wherein said adhesive is a water-soluble polymer.

45. The article of claim 44, wherein said fluid is an aqueous fluid.

46. The article of claim 45, wherein said filler is maltodextrin.

47. The article of claim 46, wherein said adhesive is selected from the group consisting of selected from the group consisting of polyethylene glycol, sodium polyacrylate, polyvinyl alcohol, polyvinyl pyrrolidone, sodium polyacrylate copolymer with maleic acid, and polyvinyl pyrrolidone copolymer with vinyl acetate.

48. The article of claim 1, wherein each layer of the article is adhered to an adjacent layer of the article via adhesive bonds provided by the activated adhesive.

49. The article of claim 1, wherein the first fibrous component is a reinforcing fibrous component restricted to a length about equal to a thickness of the layer.

50. The article of claim 49, wherein the mixture further comprises a second fibrous component, to provide dimensional stability.

51. The article of claim 50, wherein the second fibrous component has a length less than half the length of the first fibrous component.

52. An article, comprising;

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

an adhesive;

a filler; and

an aqueous fluid that activates said adhesive to form an essentially solid article composed of said plurality of particles;

said adhesive substantially soluble in, and said filler sparingly soluble in, said aqueous fluid;

the article further comprising adjacent layers, each layer comprising the product of the mixture of particles and having a contour with an edge, and a final shape of the article being defined by the edge of each of the layers, wherein either a portion of the edge of a first layer is offset from a portion of the edge of an adjacent layer to form an article having an undercut and/or overhang, or a continuous first layer is provided with a discontinuous adjacent layer to form an article having a cavity.

53. The article of claim 52, wherein said mixture comprises a first fibrous component.

54. The article of claim 53, wherein said mixture comprises a second fibrous component.

55. The article of claim 54, wherein said first fibrous component has a mean length of about 60 microns to about 200 microns.

56. The article of claim 55, wherein said second fibrous component has a mean length of about 30 μ

m to about 100 μ

m.

57. The article of claim 56, wherein said first fibrous component and said second fibrous component are selected from the group consisting of polymeric fiber, ceramic fiber, graphite fiber and fiberglass.

58. The article of claim 57, wherein said first fibrous component and said second fibrous component are a polymeric fiber selected from the group consisting of cellulose and cellulose derivatives and substituted or unsubstituted, straight or branched, alkyl or alkene, monomers containing up to eight carbon atoms.

59. The article of claim 58, wherein said filler is a carbohydrate.

60. The article of claim 59, wherein said filler is maltodextrin having a dextrose equivalent of 10.

61. The article of claim 58, wherein said filler is a polymer.

62. The article of claim 61, wherein said filler is a polymer selected from the group consisting of polyethylene glycol, sodium polyacrylate, polyvinyl alcohol, polyvinyl pyrrolidone, sodium polyacrylate copolymer with maleic acid, and polyvinyl pyrrolidone copolymer with vinyl acetate.

63. The article of claim 62, wherein said polymer is a carbohydrate selected from the group comprising acacia gum, locust bean gum, pregelatinized starch, acid-modified starch, hydrolyzed starch, sodium carboxymethylcellulose, sodium alginate, hydroxypropyl cellulose, and hydrolyzed starch.

64. The article of claim 52, wherein said filler is an organic compound.

65. The article of claim 64, wherein said filler is an organic compound selected from the group consisting of sugars, sugar alcohols, organic acids and urea.

66. The article of claim 52, wherein said filler is a protein.

67. The product of claim 66, wherein said filler is a protein selected from the group consisting of gelatin, rabbit-skin glue and soy protein.

68. The article of claim 52, wherein said filler is an inorganic compound.

69. The article of claim 68, wherein said filler is an inorganic compound selected from the group consisting of sodium silicate, plaster, bentonite and salt.

70. The article of claim 52, wherein said adhesive is a water-soluble polymer.

71. The article of claim 70, wherein said adhesive is a water soluble polymer that is a carbohydrate selected from the group comprising acacia gum, locust bean gum, pregelatinized starch, acid-modified starch, hydrolyzed starch, sodium carboxymethylcellulose, sodium alginate, hydroxypropyl cellulose, and hydrolyzed starch.

72. The article of claim 52, wherein said adhesive is an organic compound.

73. The article of claim 52, wherein said adhesive is an organic compound selected from the group consisting of sugars, sugar alcohols, organic acids and urea.

74. The product of claim 52, wherein said adhesive is a protein.

75. The product of claim 74, wherein said adhesive is a protein selected from the group consisting of gelatin, rabbit-skin glue and soy protein.

76. The article of claim 52, wherein said adhesive is an inorganic compound.

77. The article of claim 66, wherein said adhesive is an inorganic compound selected from the group consisting of sodium silicate, plaster, bentonite and salt.

78. The article of claim 52, wherein said fluid further comprises a humectant.

79. The article of claim 52, wherein said fluid further comprises a flowrate enhancer.

80. The article of claim 52, further comprising a printing aid to reduce distortion in activated material.

81. The article of claim 52, wherein said particles each comprise said filler coated with said adhesive, said mixture self-adhering when activated by said fluid.

82. The article of claim 52, wherein said mixture comprises a first and second polymeric fibrous component.

83. The article of claim 82, wherein said filler is a water-soluble polymer.

84. The article of claim 83, wherein said adhesive is a water-soluble polymer.

85. The article of claim 84, wherein said filler is maltodextrin.

86. The article of claim 85, wherein said adhesive is selected from the group consisting of selected from the group consisting of polyethylene glycol, sodium polyacrylate, polyvinyl alcohol, polyvinyl pyrrolidone, sodium polyacrylate copolymer with maleic acid, and polyvinyl pyrrolidone copolymer with vinyl acetate.

87. An article, comprising;

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

an adhesive;

a filler;

a first fibrous component; and

an aqueous fluid that activates said adhesive to form an essentially solid article composed of said plurality of particles;

said adhesive substantially soluble in, and said fiber sparingly soluble in, said aqueous fluid;

the article further comprising adjacent layers, each layer comprising the product of the mixture of particles and having a contour with an edge, and a final shape of the article being defined by the edge of each of the layers, wherein either a portion of the edge of a first layer is offset from a portion of the edge of an adjacent layer to form an article having an undercut and/or overhang, or a continuous first layer is provided with a discontinuous adjacent layer to form an article having a cavity.

88. The article of claim 87, wherein said filler is sparingly soluble in said aqueous fluid.