IP Library Granted Patent US 7,455,804
Granted Patent B2
US 7,455,804 · App. 10/399,444 · Granted Nov 25, 2008

Three-dimensional structured printing

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Quick Facts
Patent No.
US 7,455,804
App. No.
10/399,444
Granted
Nov 25, 2008
Kind
B2
Abstract

A process for forming a three-dimensional article in sequential layers in accordance with a digital model of the article. The process comprises the steps of defining a layer of powder material, applying a liquid reagent to the powder layer in a pattern corresponding to the digital model, and repeating these steps to form successive layers. The powder comprises a first reactive component and the liquid includes a second active component capable of reacting with the first reactive component so that the article is built up in layers.

Claims (76)

1. A process for forming a three-dimensional article in sequential cross-sectional layers in accordance with a model of the article, the process comprising the steps of:

defining a layer of powder material;

applying a liquid reagent to the powder layer in a pattern corresponding to a respective cross-sectional layer of the model; and

repeating these steps to form successive layers;

wherein the powder comprises a first reactive component selected from an organic or organometallic polymer, oligomer or monomer and the liquid reagent includes a second active component comprising an oxetane, the second active component causing a polymerization reaction to take place in said layer by chemically reacting with said first reactive component within the powder to form a new chemical component, and thereby to form substantially void-free regions in the article where the liquid reagent has been applied to the powder material and wherein the article which is formed has a tensile strength of greater than about 25 MPa.

2. The process of claim 1 wherein the polymerization reaction is a cross-linking polymerization reaction.

3. The process of claim 1 wherein the powder material includes an organic or inorganic filler, a pigment, nanoparticles, a dye, or a surfactant.

4. The process of claim 1 wherein the powder material comprises a thermoplastic material, a surface treated powder, or a thermosetting powder.

5. The process of claim 4 wherein the thermoplastic material is a polyvinylacetal.

6. The process of claim 4 wherein the surface treated powder is a treated polypropylene, ABS, or polycarbonate.

7. The process of claim 4 wherein the thermosetting powder is an epoxy powder.

8. The process of claim 1 wherein the powder material is a polyacrylic acid, poly(acrylonitrile-co-butadiene), poly(allylamine), polyacrylic resin with a functional acrylate group, polybutadiene, epoxy functionalized butadiene, poly(glycidylmeth)acrylate, polyTHF, polycaprolactone diol, HEMA, HEA, maleic anhydride polymer, polyvinylbutyral, polyvinyl alcohol, poly(4-vinylphenol), a copolymer or blend of the foregoing, or any of the foregoing compounds endcapped with an epoxy, vinyl ether, acrylate/methacrylate, hydroxy, amine, or vinyl moiety.

9. The process of claim 1 wherein the second active component is a compound which undergoes a condensation reaction.

10. The process of claim 9 wherein said condensation reaction is initiated by an electromagnetically triggered system.

11. The process of claim 1 wherein said liquid reagent has a viscosity of less than about 40 cps.

12. The process of claim 1 wherein said liquid reagent has a viscosity in the range of about 2-30 cps.

13. The process of claim 1 wherein said liquid reagent has a viscosity below 15 cps.

14. The process of claim 1 wherein said liquid reagent includes a viscosity lowering diluent.

15. The process of claim 14 wherein said diluent has reactive groups for swelling or dissolving the powder material.

16. The process of claim 14 wherein said diluent comprises about 30 to 60% by volume of said liquid reagent.

17. The process of claim 14 wherein said diluent is reactive.

18. The process of claim 1 wherein said powder substantially comprises the first reactive component.

19. The process of claim 1 wherein said model is a digital model.

20. The process of claim 1 wherein at least two of said successive layers comprise different materials.

21. The process of claim 1 wherein a plurality of different liquid reagents are applied to respective powder layers.

22. The process of claim 1 wherein a plurality of different liquid reagents are applied to a single powder layer.

23. The process of claim 1 wherein said plurality of different liquid reagents are applied by a device having a plurality of nozzles in a single pass of said device over said layer.

24. The process of claim 1 wherein the different liquid reagents are applied in respective sequential passes of said device over said layer.

25. The process of claim 1 wherein the layers have differing thicknesses.

26. The process of claim 1 wherein a layer is formed having varying thickness over its extent.

27. The process of claim 1 further comprising irradiating the article with electromagnetic radiation.

28. The process of claim 27 wherein the article is irradiated with UV radiation.

29. The process of claim 1 further comprising irradiating the powder layer with electromagnetic radiation after applying said liquid reagent and prior to defining a next layer of powder material.

30. The process of claim 29 wherein the electromagnetic radiation is UV radiation.

31. The process of claim 1 wherein said liquid reagent is applied to said powder layer through a plurality of nozzles.

32. The process of claim 31 wherein said nozzles form a part of an inkjet print head.

33. The process of claim 31 wherein said nozzles include openings in the range of about 0.01 to about 100 μm.

34. The process of claim 31 wherein said nozzles produce droplets of said liquid reagent having a diameter in the range of about 0.1 to about 200 μm.

35. The process of claim 1 wherein said liquid reagent is colored.

36. The process of claim 1 wherein said liquid reagent includes colloidal or nano-sized particles, organic core-shells, metals, or alloys.

37. The process of claim 1 wherein said liquid reagent is applied at a temperature in the range of 65-75° C.

38. The process of claim 1 wherein each of said layers has a thickness in the range of about 1.0 to 30 μm.

39. The process of claim 1 wherein each formed layer has a thickness in the range of about 1.0 to 200 μm.

40. The process of claim 1 wherein all of the liquid reagent which is applied to the powder layer is incorporated into said three-dimensional article.

41. The process of claim 1 wherein the first reactive component is a compound having reactive hydroxyl or acetal groups.

42. The process of claim 1 wherein the article includes seamless bonds between successive layers.

43. A process for forming sequential cross-sectional layers of a three-dimensional article comprising:

defining a layer of powder material;

through a plurality of nozzles, applying a liquid reagent to the powder layer in a pattern corresponding to a respective cross-sectional layer of the model;

repeating these steps to form successive layers;

wherein the powder comprises a first reactive component selected from an organic or organometallic polymer, oligomer or monomer and the liquid reagent includes a second active component comprising an oxetane, the second active component causing a polymerization reaction to take place in said layer by chemically reacting with said first reactive component within the powder to form a new chemical component, and thereby to form substantially void-free regions of high strength in the article where the liquid reagent has been applied to the powder material and wherein the article which is formed has a tensile strength of greater than about 25 MPa.

44. The process of claim 43 further comprising irradiating said article with electromagnetic radiation.

45. The process of claim 43 further comprising irradiating said article with UV radiation.

46. The process of claim 43 further comprising irradiating the powder layer with UV radiation after applying said liquid reagent and prior to defining a next powder layer.

47. The process of claim 43 wherein the polymerization reaction is a cross-linking polymerization reaction.

48. The process of claim 43 wherein the first reactive component is a compound having reactive hydroxyl or acetal groups.

49. The process of claim 43 wherein the liquid reagent has a viscosity in the range of about 2-30 cps.

50. The process of claim 43 wherein the liquid includes a viscosity-lowering diluent.

51. The process of claim 43 wherein said article which is formed has an elongation modulus of at least about 5%.

52. The process of claim 43 wherein the article which is formed is transparent.

53. The process of claim 43 wherein the article includes seamless bonds between successive layers.

54. A process for forming a substantially void-free three-dimensional article in sequential cross-sectional layers in accordance with a model of the article, the process comprising the steps of:

defining a layer of powder material;

via a plurality of micro-fine nozzles, jetting a liquid reagent onto the powder layer in a pattern corresponding to a respective cross-sectional layer of the model, said liquid reagent dissolving the powder material which comes into contact with it;

repeating these steps to form successive layers;

wherein the powder comprises a first reactive component selected from an organic or organometallic polymer, oligomer or monomer and the liquid reagent includes a second active component comprising an oxetane, the second active component causing a polymerization reaction to take place in said layer by chemically reacting with said first reactive component within the powder to form a new chemical component, and thereby forming substantially void-free regions of high strength in the article where the liquid reagent has been jetted on the powder layer and wherein the article which is formed has a tensile strength of greater than about 25 MPa.

55. The process of claim 54 further comprising irradiating said article with electromagnetic radiation.

56. The process of claim 54 further comprising irradiating said article with UV radiation.

57. The process of claim 54 further comprising irradiating the powder layer with UV radiation after applying said liquid reagent and prior to defining a next powder layer.

58. The process of claim 54 wherein the polymerization reaction is a cross-linking polymerization reaction.

59. The process of claim 54 wherein the first reactive component is a compound having reactive hydroxyl or acetal groups.

60. The process of claim 54 wherein the liquid reagent has a viscosity in the range of about 2-30 cps at room temperature.

61. The process of claim 54 wherein the liquid includes a viscosity-lowering diluent.

62. The process of claim 54 wherein said article which is formed has an elongation modulus of at least about 5%.

63. The process of claim 54 wherein the article which is formed is transparent.

64. The process of claim 54 wherein the article includes seamless bonds between successive layers.

Assignments (9)
RELEASE OF SECURITY INTEREST Recorded Aug 26, 2021
From: HSBC BANK USA, NATIONAL ASSOCIATION
To: 3D SYSTEMS, INC.
Reel/Frame 057651/0374 →
SECURITY INTEREST Recorded Feb 27, 2019
From: 3D SYSTEMS, INC.
To: HSBC BANK USA, NATIONAL ASSOCIATION, AS ADMINISTRATIVE AGENT
Reel/Frame 048456/0017 →
TERMINATION AND RELEASE OF SECURITY INTEREST IN UNITED STATES TRADEMARKS AND PATENTS Recorded Jun 13, 2018
From: JPMORGAN CHASE BANK, N.A.
To: HUNTSMAN ADVANCED MATERIALS AMERICAS INC. (N/K/A HUNTSMAN ADVANCED MATERIALS AMERICAS LLC)
Reel/Frame 046352/0893 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Nov 29, 2012
From: HUNTSMAN ADVANCED MATERIALS AMERICAS LLC
To: HUNTSMAN INTERNATIONAL LLC
Reel/Frame 029370/0038 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Dec 9, 2011
From: HUNTSMAN INTERNATIONAL LLC
To: 3D SYSTEMS, INC.
Reel/Frame 027355/0090 →
CORRECTIVE ASSIGNMENT TO CORRECT THE NATURE OF CONVEYANCE FROM ASSIGNMENT TO SECURITY AGREEMENT PREVIOUSLY RECORDED ON REEL 025855 FRAME 0192. ASSIGNOR(S) HEREBY CONFIRMS THE ASSIGNMENT. Recorded Jun 28, 2011
From: DEUTSCHE BANK TRUST AG NEW YORK BRANCH, AS RESIGNING ADMINISTRATIVE AGENT AND COLLATERAL AGENT
To: JPMORGAN CHASE BANK, N.A., AS COLLATERAL AGENT
Reel/Frame 026515/0735 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 28, 2011
From: DEUTSCHE BANK TRUST AG NEW YORK BRANCH, AS RESIGNING ADMINISTRATIVE AGENT AND COLLATERAL AGENT
To: JPMORGAN CHASE BANK, N.A., AS COLLATERAL AGENT
Reel/Frame 025855/0192 →
TERMINATION OF SECURITY INTEREST Recorded Jan 19, 2006
From: DEUTSCHE BANK AG NEW YORK BRANCH, AS AGENT
To: VANTICO INC. AND VANTICO A&T U S INC. (NOW KNOWN AS HUNTSMAN ADVANCED MATERIALS AMERICAS INC.)
Reel/Frame 017996/0648 →
TERMINATION OF SECURITY INTEREST Recorded Jan 19, 2006
From: DEUTSCHE BANK AG NEW YORK BRANCH, AS AGENT
To: VANTICO INC. AND VANTICO A&T U S INC. (NOW KNOWN AS HUNTSMAN ADVANCED MATERIALS AMERICAS INC.)
Reel/Frame 018047/0836 →