Additive manufacturing of hierarchical three- dimensional micro-architected aerogels

Patent metadata

Field	Value
Publication number	US-11884002-B2
Application number	US-201917049934-A
Country	US
Kind code	B2
Filing date	Apr 5, 2019
Priority date	Apr 24, 2018
Publication date	Jan 30, 2024
Grant date	Jan 30, 2024

Abstract

Disclosed here is a method for making a three-dimensional micro-architected aerogel, comprising: (a) curing a reaction mixture comprising a co-sol-gel material (e.g., graphene oxide (GO)) and at least one catalyst to obtain a crosslinked co-sol-gel (e.g., GO hydrogel); (b) providing a photoresin comprising a solvent, a photoinitiator, a crosslinkable polymer precursor, and a dispersion of the crosslinked co-sol-gel (e.g., GO hydrogel); (c) curing the photoresin using projection microstereolithography layer-by-layer to produce a wet gel having a pre-designed three-dimensional structure; (d) drying the wet gel to produce a dry gel; and (e) pyrolyzing the dry gel to produce a three-dimensional micro-architected aerogel (e.g., graphene aerogel). Also disclosed is a photoresin for projection microstereolithography, comprising a solvent, a photoinitiator, a crosslinkable polymer precursor, and a dispersion of a crosslinked co-sol-gel.

First claim

What is claimed is:

1. A method for making a three-dimensional micro-architected aerogel, comprising:
(a) curing a reaction mixture comprising a co-sol-gel material and at least one catalyst to obtain a crosslinked co-sol-gel, wherein step (a) comprises curing the reaction mixture at a temperature of 100° C. or less;
(b) providing a photoresin comprising a solvent, a photoinitiator, a crosslinkable polymer precursor, and a dispersion of the crosslinked co-sol-gel;
(c) curing the photoresin using projection microstereolithography layer-by-layer to produce a wet gel having a pre-designed three-dimensional structure;
(d) drying the wet gel to produce a dry gel; and
(e) pyrolyzing the dry gel to produce a three-dimensional micro-architected aerogel.

2. The method of claim 1 , wherein the co-sol-gel material is graphene oxide (GO), resorcinol formaldehyde (RF), melamine formaldehyde (MF), or a metal organic framework (MOF).

3. The method of claim 1 , wherein the solvent comprises an organic solvent.

4. The method of claim 1 , wherein the solvent comprises N,N-dimethylformamide (DMF).

5. The method of claim 1 , wherein the photoinitiator is soluble in an organic solvent.

6. The method of claim 1 , wherein the photoinitiator comprises phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (Irg819).

7. The method of claim 1 , wherein the crosslinkable polymer precursor comprises a non-aromatic acrylate prepolymer and an aromatic acrylate prepolymer, and wherein the crosslinkable polymer precursor accounts for about 12-30 wt. % of the photoresin.

8. The method of claim 1 , wherein the crosslinkable polymer precursor comprises polyethylene glycol diacrylate (PEGDA) and Bisphenol A ethoxylate (2 EO/phenol) dimethacrylate (BisA-EDMA).

9. The method of claim 1 , wherein the catalyst comprises ammonium hydroxide.

10. The method of claim 1 , wherein step (c) comprises curing the photoresin at a wavelength of 500 nm or less.

11. The method of claim 1 , wherein step (e) comprises pyrolyzing in an inert environment at a temperature of 800° C. or more.

12. The method of claim 1 , further comprising the step of (f) CO 2 etching the three-dimensional micro-architected aerogel.

13. A method for making a three-dimensional micro-architected aerogel, comprising:
(a) curing a reaction mixture comprising a co-sol-gel material and at least one catalyst to obtain a crosslinked co-sol-gel;
(b) providing a photoresin comprising a solvent, a photoinitiator, a crosslinkable polymer precursor, and a dispersion of the crosslinked co-sol-gel;
(c) curing the photoresin using projection microstereolithography layer-by-layer to produce a wet gel having a pre-designed three-dimensional structure;
(d) drying the wet gel to produce a dry gel; and
(e) pyrolyzing the dry gel to produce a three-dimensional micro-architected aerogel,
wherein step (b) comprises washing the crosslinked co-sol-gel by solvent exchange, dispersing the crosslinked co-sol-gel in the solvent by sonication, and adding the photoinitiator and the crosslinkable polymer precursor to the dispersion of the crosslinked co-sol-gel.

14. A method for making a three-dimensional micro-architected aerogel, comprising:
(a) curing a reaction mixture comprising a co-sol-gel material and at least one catalyst to obtain a crosslinked co-sol-gel;
(b) providing a photoresin comprising a solvent, a photoinitiator, a crosslinkable polymer precursor, and a dispersion of the crosslinked co-sol-gel;
(c) curing the photoresin using projection microstereolithography layer-by-layer to produce a wet gel having a pre-designed three-dimensional structure;
(d) drying the wet gel to produce a dry gel; and
(e) pyrolyzing the dry gel to produce a three-dimensional micro-architected aerogel,
wherein step (d) comprises solvent exchange, supercritical drying, and/or freeze drying.

Assignees

• L Livermore Nat Security Llc
• Virginia Polytechnic Institute And State Univ

Inventors

• Worsley Marcus A
• Zheng Xiaoyu
• Campbell Patrick G
• Duoss Eric
• Oakdale James
• Spadaccini Christopher
• HENSLEIGH Ryan

Classifications

• B29C64/124 Primary

  using layers of liquid which are selectively solidified · CPC title

• B01J13/0091

  Preparation of aerogels, e.g. xerogels · CPC title

• B29C64/30

  Auxiliary operations or equipment · CPC title

• B33Y10/00

  Processes of additive manufacturing · CPC title

• B33Y40/20

  Post-treatment, e.g. curing, coating or polishing · CPC title