IP Library Granted Patent US 12,351,718
Granted Patent B2
US 12,351,718 · App. 16/212,525 · Granted Jul 8, 2025

Engineered feedstocks for additive manufacture of glass

Inventors: Rebecca Dylla-Spears (Dublin, CA); Theodore F. Baumann (Discovery Bay, CA); Eric B. Duoss (Dublin, CA); Joshua D. Kuntz (Livermore, CA); Robin Miles (San Ramon, CA); Du Nguyen (Fremont, CA); Christopher Spadaccini (Oakland, CA); Tayyab I. Suratwala (Pleasanton, CA); Timothy Dexter Yee (Alameda, CA); Cheng Zhu (Livermore, CA); Cameron David Meyers (Minneapolis, MN); Nikola Dudukovic (Hayward, CA); Tyler Fears (Pleasanton, CA); Fang Qian (Santa Cruz, CA); Koroush Sasan (Pleasanton, CA); Joel Destino (Omaha, NE)
Assignee: Lawrence Livermore National Security, LLC
C09D11/03B33Y10/00B33Y70/00C03B19/01C09D1/00C09D11/02C09D11/033
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Quick Facts
Patent No.
US 12,351,718
App. No.
16/212,525
Granted
Jul 8, 2025
Kind
B2
Abstract

According to one embodiment, a method includes forming a structure by printing an ink, the ink including a glass-forming material, and heat treating the formed structure for converting the glass-forming material to glass. According to another embodiment, an ink composition includes a glass-forming material and a solvent.

Claims (79)

1. An ink composition, comprising:

a glass-forming material configured to be densified to a glass form,

wherein the glass-forming material consists essentially of inorganic particles of a single composition; and

a solvent.

2. The ink composition of claim 1 , wherein the single composition is chosen from: fumed silica, colloidal silica, LUDOX colloidal silica dispersion, titania particles, zirconia particles, alumina particles, and metal chalcogenide particles.

3. The ink composition of claim 1 , wherein the glass-forming material includes a silica polymer.

4. The ink composition of claim 1 , further comprising an effective amount of a second component for altering a property of a glass structure created using the ink.

5. The ink composition of claim 4 , wherein the second component affects the property chosen from: an optical characteristic, a mechanical characteristic, a magnetic characteristic, a thermal characteristic, an electrical characteristic, and a chemical characteristic.

6. The ink composition of claim 4 , wherein the second component is a color altering component chosen from: metal nanoparticles, sulfur, metal sulfide, metal chloride, and metal oxide.

7. The ink composition of claim 4 wherein the second component is an absorptivity altering component chosen from: cerium oxide, iron, copper, chromium, silver, and gold.

8. The ink composition of claim 4 , wherein the second component is a refractive index altering component chosen from: titanium, zirconium, aluminum, lead, thorium, barium.

9. The ink composition of claim 4 , wherein the second component is a dispersion altering component chosen from: barium and thorium.

10. The ink composition of claim 4 , wherein the second component is an attenuation and/or optical density altering component chosen: an alkaline metal and an alkaline earth metal.

11. The ink composition of claim 4 , wherein the second component is a photosensitivity altering component chosen from: silver, cerium, and fluorine.

12. The ink composition of claim 4 , wherein the second component is an electrical conductivity altering component chosen from: alkali metal ions, fluorine, and carbon nanotubes.

13. The ink composition of claim 4 , wherein the second component is a birefringence altering component chosen from: titanium, zirconium, zinc, niobium, strontium, lithium, in combination with silicon and oxygen.

14. The ink composition of claim 4 , wherein the second component is a thermal conductivity altering component chosen from: a metal and carbon nanotubes.

15. The ink composition of claim 4 , wherein the second component is a thermal emissivity altering component chosen from: tin oxide and iron.

16. The ink composition of claim 4 , wherein the second component is a thermal expansion altering component chosen from: boron oxide and titanium oxide.

17. The ink composition of claim 4 , wherein the second component is sodium carbonate for altering a glass transition temperature of the glass structure.

18. The ink composition of claim 4 , wherein the second component is a melting point altering component chosen from: sodium, aluminum, and lead.

19. The ink composition of claim 4 , wherein the second component is a gain coefficient altering component chosen from: rare earth ions and transition metal ions.

20. The ink composition of claim 4 , wherein the second component affects a property chosen from: photoemission, luminescence, and fluorescence.

21. The ink composition of claim 4 , wherein the second component is a chemical reactivity altering component chosen from: an alkaline metal, an alkaline earth metal, and silver.

22. The ink composition of claim 4 , wherein the second component is a density altering component chosen from: titanium, zirconium, aluminum, lead, thorium, and barium.

23. The ink composition of claim 1 , further comprising an effective amount of an additive for causing an effect chosen from: enhancing dispersion, enhancing phase stability, enhancing network strength, controlling pH, changing pH, modifying rheology, reducing crack formation during drying, inhibiting crystallization, and aiding in sintering.

24. The ink composition of claim 1 , further comprising an effective amount of an additive for enhancing dispersion, the additive being chosen from: a surfactant, a polyelectrolyte, and an inorganic acid.

25. The ink composition of claim 1 , further comprising an effective amount of an additive for enhancing phase stabilization.

26. The ink composition of claim 1 , further comprising an effective amount of an additive for inhibiting crystallization, the additive being chosen from: B 2 O 3 , Al 2 O 3 and Ga 2 O 3 .

27. The ink composition of claim 1 , wherein the glass-forming material is present in the range of about 5 vol % to about 50 vol % based on a total volume of the ink composition, the solvent is present in the range of about 30 vol % to about 95 vol % based on the total volume of the ink composition; and further comprising one or more second components present in the range of 0 wt % to about 20 wt % based on the total volume of the ink composition; and one or more additives present in the range of from 0 wt % to about 10 wt % based on the total volume of the ink composition.

28. The ink composition of claim 1 , wherein the glass-forming material includes an inorganic polymer.

29. The ink composition of claim 1 , wherein the ink is configured to be printed into a low density form having the glass-forming material and densified into a glass form.

30. The ink composition of claim 29 , wherein the low density form is porous and amorphous.

31. The ink composition of claim 1 , wherein the ink is configured to be printed and densified into a glass form.

32. The ink composition of claim 1 , wherein the composition is configured to form a three-dimensional structure that is self-supporting.

33. The ink composition of claim 1 , wherein the composition is a resin for a stereolithography printing technique.

34. The ink composition of claim 1 , wherein the composition is an ink for an extrusion-based additive manufacturing process.

35. The ink composition of claim 1 , wherein the composition is a powder for a laser melting additive manufacturing process.

36. An ink composition comprising:

a glass-forming material; and

a solvent, wherein-the glass-forming material includes intermixed particles, wherein an average diameter of the intermixed particles is in a range of about 100 nanometers to about 400 nanometers.

37. The ink composition of claim 36 , wherein the glass-forming material includes a silica-germanium oxide polymer.

38. The ink composition of claim 36 , wherein the glass-forming material includes a metal-containing organic precursor and/or a metal-containing inorganic precursor.

39. The ink composition of claim 38 wherein the precursor is chosen from: metalalkoxides, siloxanes, silicates, phosphates, chalcogenides, metal-hydroxides, metal salts.

40. The ink composition of claim 36 , wherein the glass-forming material includes blended particles having the intermixed particles and at least one other type of particle having a different composition than the intermixed particles,

wherein the at least one other type of particle is chosen from: core-shell particles, particles having a single composition, layered shell particles having an onion structure comprising layers of different compositions, hollow layered shell particles including a hollow space in core locations, core-shell particles with an intermixed core, and layered shell particles with an intermixed core.

41. The ink composition of claim 40 , wherein the blended particles include silica lead oxide.

42. The ink composition of claim 40 , wherein the at least one other type of particle is a core-shell particle.

43. The ink composition of claim 42 , wherein an average diameter of a core particle of the core-shell particles is in a range of about 25 nanometers to about 200 nanometers.

44. The ink composition of claim 42 , wherein an average thickness of a shell of the core-shell particles is in a range of about 2 nanometers to about 4 nanometers.

45. The ink composition of claim 36 , wherein the glass-forming material includes a combination particle having a core being an intermixed particle and at least one feature chosen from: a shell, a layered shell, and an inorganic polymer.

46. The ink composition of claim 36 , wherein the glass-forming material includes a polymer.

47. The ink composition of claim 36 , wherein the glass-forming material includes a silica-containing polymer.

48. The ink composition of claim 36 , wherein the ink is configured to be printed into a low density form having the glass-forming material and densified into a glass form.

49. The ink composition of claim 48 , wherein the low density form is porous and amorphous.

50. The ink composition of claim 36 , wherein the composition is configured to form a three-dimensional structure that is self-supporting.

51. The ink composition of claim 36 , wherein the composition is a resin for a stereolithography printing technique.

52. The ink composition of claim 36 , wherein the composition is an ink for an extrusion-based additive manufacturing process.

53. The ink composition of claim 36 , wherein the composition is a powder for a laser melting additive manufacturing process.

54. The ink composition of claim 36 , wherein the intermixed particles comprise clusters of oligomer-based particles, each inter-mixed particle comprising at least two different chemical species.

55. The ink composition of claim 36 , further comprising an effective amount of a second component for altering a property of a glass structure created using the ink.

56. The ink composition of claim 55 , wherein the second component affects a property chosen from: an optical characteristic, a mechanical characteristic, a magnetic characteristic, a thermal characteristic, an electrical characteristic, and a chemical characteristic.

57. An ink composition comprising:

a glass-forming material; and

a solvent,

wherein the glass-forming material includes layered shell particles,

wherein each layered shell particle includes at least two shell layers above a core particle, wherein one of the at least two shell layers has a different composition than the other of the at least two shell layers.

58. The ink composition of claim 57 , wherein the layered shell particles include silica-germanium oxide particles.

59. The ink composition of claim 57 wherein the glass-forming material includes hollow layered shell particles.

60. The ink composition of claim 57 , wherein the ink is configured to be printed and densified into a glass form.

61. The ink composition of claim 57 , wherein the ink is configured to be printed into a low density form having the glass-forming material and densified into a glass form.

62. The ink composition of claim 61 , wherein the low density form is porous and amorphous.

63. The ink composition of claim 57 , wherein the composition is configured to form a three-dimensional structure that is self-supporting.

64. The ink composition of claim 57 , wherein the composition is a resin for a stereolithography printing technique.

65. The ink composition of claim 57 , wherein the composition is an ink for an extrusion-based additive manufacturing process.

66. The ink composition of claim 57 , wherein the composition is a powder for a laser melting additive manufacturing process.

67. The ink composition of claim 57 , further comprising an effective amount of a second component for altering a property of a glass structure created using the ink.

68. The ink composition of claim 67 , wherein the second component affects a property chosen from: an optical characteristic, a mechanical characteristic, a magnetic characteristic, a thermal characteristic, an electrical characteristic, and a chemical characteristic.

69. The ink composition of claim 67 , wherein the second component is a color altering component chosen from: metal nanoparticles, sulfur, metal sulfide, metal chloride, and metal oxide.

Assignments (2)
CONFIRMATORY LICENSE (SEE DOCUMENT FOR DETAILS) Recorded Sep 4, 2020
From: LAWRENCE LIVERMORE NATIONAL SECURITY, LLC
To: U.S. DEPARTMENT OF ENERGY
Reel/Frame 053707/0645 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Sep 16, 2019
From: DYLLA-SPEARS, REBECCA; BAUMANN, THEODORE F.; DUOSS, ERIC B.; KUNTZ, JOSHUA D.; MILES, ROBIN; NGUYEN, DU; SPADACCINI, CHRISTOPHER; SURATWALA, TAYYAB I.; YEE, TIMOTHY DEXTER; ZHU, CHENG; MEYERS, CAMERON DAVID; DUDUKOVIC, NIKOLA; FEARS, TYLER; QIAN, FANG; SASAN, KOROUSH; DESTINO, JOEL
To: LAWRENCE LIVERMORE NATIONAL SECURITY, LLC
Reel/Frame 050387/0096 →
Continuity (3)
Continuation In Part PCTUS2017036197 · Jun 6, 2017
Provisional Application 62346228 · Jun 6, 2016
Related Publication 20200024465A1 · Jan 23, 2020
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