Three dimensional porous siloxanes using leachable porogen particles

Patent metadata

Field	Value
Publication number	US-12077672-B2
Application number	US-202117499641-A
Country	US
Kind code	B2
Filing date	Oct 12, 2021
Priority date	Mar 28, 2019
Publication date	Sep 3, 2024
Grant date	Sep 3, 2024

Abstract

A product of additive manufacturing with a silicone-based ink includes a plurality of continuous filaments comprised of a siloxane matrix, wherein the continuous filaments are arranged in a geometric pattern, a plurality of inter-filament pores defined by the geometric pattern of the continuous filaments, and a plurality of intra-filament pores having an average diameter in a range of greater than 1 micron to less than 50 microns.

First claim

What is claimed is:

1. A product of additive manufacturing with a silicone-based ink, the product comprising:
at least one continuous filament comprised of a siloxane matrix having a treated silica hydrophobic reinforcing filler therein, wherein the continuous filaments are arranged in a geometric pattern;
a plurality of inter-filament pores, wherein the inter-filament pores are defined by the geometric pattern of the at least one continuous filament; and
a plurality of intra-filament pores, wherein the intra-filament pores have an average diameter in a range of greater than 1 micron to less than 50 microns, wherein the intra-filament pores are present as an open interconnected network of intra-filament pores.

2. The product as recited in claim 1 , wherein the siloxane matrix includes vinyl terminated siloxane polymers.

3. The product as recited in claim 1 , wherein the product is a three-dimensional silicone-based structure, wherein the continuous filaments of the three-dimensional structure have an average diameter greater than about 100 microns.

4. The product as recited in claim 1 , wherein the product is a three-dimensional silicone-based structure having inter-filament pores interconnected from a surface of the three-dimensional silicone-based structure to a surface on an opposite side of the three-dimensional silicone-based structure.

5. The product as recited in claim 1 , wherein the intra-filament pores are interconnected from a surface of the associated filament to a surface on an opposite side of the associated filament.

6. A method of forming the product as recited in claim 1 , wherein the product is a three-dimensional printed siloxane-containing structure having intra-filament porosity, the method comprising:
extruding at least one continuous filament of a mixture through a nozzle to form a structure having at least one continuous filament,
the mixture comprising a vinyl-terminated siloxane macromer, the hydrophobic filler, a rheology modifying additive, and a plurality of porogen particles;
curing the extruded mixture to at least a predefined extent to form the three-dimensional printed siloxane structure; and
removing the porogen particles from the three-dimensional printed siloxane structure.

7. The method as recited in claim 6 , wherein the mixture includes a curing agent and a crosslinking agent.

8. The method as recited in claim 7 , wherein the mixture includes an inhibitor present in an effective amount to control a rate of curing by the curing agent.

9. The method as recited in claim 6 , wherein the hydrophobic filler is treated silica.

10. The method as recited in claim 6 , wherein the porogen particles are soluble in an aqueous solution.

11. The method as recited in claim 6 , wherein a range of a ratio of an average diameter of the porogen particles to a diameter of the nozzle is about 1:5 to about 1:20.

12. The method as recited in claim 6 , wherein an average diameter of the porogen particles is in a range greater than one micron to about 50 microns.

13. The method as recited in claim 6 , wherein an average diameter of the porogen particles is in a range of greater than 10 microns to about 30 microns.

14. The method as recited in claim 6 , wherein an average circularity of the porogen particles is greater than 0.90.

15. The method as recited in claim 6 , wherein a concentration of porogen particles is in a range of greater than 0 volume % to about 75 volume % of volume of total ink.

16. The method as recited in claim 6 , wherein removing the porogen particles comprises soaking the three-dimensional printed siloxane structure in a solution to dissolve the porogen particles.

17. The product as recited in claim 1 , wherein at least some of the intra-filament pores in a first filament of the at least one continuous filament are interconnected from a surface of the first filament to a surface on an opposite side of the first filament such that interiors of the pores are in fluidic communication with one another and the surfaces on the opposite sides of the filament.

18. A product of additive manufacturing with a silicone-based ink, the product comprising:
at least one continuous filament comprised of a siloxane matrix, wherein the at least one continuous filament is arranged in a geometric pattern;
a plurality of inter-filament pores, wherein the inter-filament pores are defined by the geometric pattern of the at least one continuous filament; and
a plurality of intra-filament pores positioned to form an open interconnected network of the intra-filament pores, wherein an average diameter of the intra-filament pores is in a range of greater than 1 micron to less than 50 microns.

Assignees

• L Livermore Nat Security Llc

Inventors

• Perez Lemuel Perez
• Duoss Eric B
• Lenhardt Jeremy
• Wilson Thomas S

Classifications

• B33Y70/10

  Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials · CPC title

• C09D11/102

  containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds · CPC title

• C08J2201/042

  Elimination of an organic solid phase · CPC title

• C08K2201/006

  Additives being defined by their surface area · CPC title

• C08K2201/003

  Additives being defined by their diameter · CPC title