Method of making silicone-based foam material and silicon-based materials formed therefrom
Disclosed herein are embodiments of a silicone-based foam material and composition and method embodiments for making the same. Also disclosed are embodiments of a silicon-based material that can be formed from the silicone-based foam material, as well as methods for making the same.
1. A method, comprising:
combining a silicone precursor, a silicon-containing crosslinker, a surfactant, a curing agent, and water to provide a multi-phasic composition;
mixing components of the multi-phasic composition to provide a silicone polymer;
removing the water to provide a co-continuous silicone-based foam material comprising (i) a first continuous phase comprising the silicone polymer, and (ii) a second continuous phase provided by one or more pores, wherein the one or more pores comprise walls that are defined by a surface of the silicone polymer and that exhibit substantially negative Gaussian curvature and a substantially zero mean curvature;
exposing the co-continuous silicone-based foam material to a first heat treatment under a gaseous atmosphere to form a co-continuous porous silicon-based material; and
exposing the co-continuous porous silicon-based material to a second heat treatment in the presence of air; wherein
the silicone precursor has a structure according to Formula I
wherein each R 1 independently is selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or an organic functional group provided by any combination of such groups; R 2 independently is selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or an organic functional group provided by any combination of such groups; each R 3 independently is hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or an organic functional group provided by any combination of such groups; each R 4 independently is hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or an organic functional group provided by any combination of such groups; n is an integer selected from 0 to 1,000,000; m is an integer selected from 1 to 1,000,000; and
the silicon-containing crosslinker has a structure according to Formula II
wherein each X independently is halogen or OR 5 , wherein each R 5 independently is aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or an organic functional group provided by any combination of such groups; and Y is
(i) OR 5 , wherein each R 5 independently is aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or an organic functional group provided by any combination of such groups;
(ii) —O—Si(X′) 3 , wherein each X′ independently is halogen or OR 5 , wherein each R 5 independently is aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or an organic functional group provided by any combination of such groups; or
(iii) hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or an organic functional group provided by any combination of such groups.
2. The method of claim 1 , further comprising:
(i) adding a filler material, a solvent other than water, or both to the multi-phasic composition; or
(ii) washing the co-continuous silicone-based foam material with a solution to remove residual curing agent after removing the water; or
(iii) both (i) and (ii).
3. The method of claim 2 , wherein:
(i) the filler material is hydrophobic silica that comprises silica treated with an oxy-silicon material having a structure according to a formula (R 10 O) 2 Si(R 11 ) 2 , such that the silica and the oxy-silicon material are bound to provide a structure having a formula Si a —O—Si(R 11 ) 2 OR 10 ;
wherein Si a represents the silica, each R 10 independently is aliphatic or aryl and each R 11 independently is aliphatic or aryl; and
(ii) wherein the solvent other than water is heptanes.
4. The method of claim 2 , wherein the solution comprises hydrogen peroxide.
5. The method of claim 1 , wherein the silicone precursor, the silicon-containing crosslinker, and the surfactant are combined to provide a first mixture and the curing agent is added to the first mixture to provide a second mixture, and then the water is added to the second mixture to provide the multi-phasic composition.
6. The method of claim 1 , wherein mixing comprises combining components of the multi-phasic composition using syringe mixing.
7. The method of claim 1 , further comprising placing the multi-phasic composition into a mold prior to removing the water.
8. The method of claim 1 , wherein removing the water comprises (i) drying the co-continuous silicone-based foam material using heat; or (ii) allowing the co-continuous silicone-based foam material to rest at ambient temperature.
9. The method of claim 1 , wherein the surfactant is selected from a sorbitan fatty acid ester; a glycerin fatty acid ester; a polyglycerin fatty acid ester; a sucrose fatty acid ester; a polyethylene glycol fatty acid ester, a polyethylene glycol sorbitan fatty acid ester, a polypropylene glycol fatty acid ester, a polypropylene glycol sorbitan fatty acid ester, or a copolymer thereof; a polyethylene glycol-polydimethylsiloxane copolymer; or a combination thereof; and the curing agent is tin(II)ethylhexanoate.
10. The method of claim 1 , wherein the co-continuous silicone-based foam material has an open-celled structure wherein at least 90% of the pores are open.
11. The method of claim 1 , wherein the first heat treatment comprises exposing the co-continuous silicone-based foam material to an environment that has a starting temperature and then increasing the temperature of the environment to a final temperature that is higher than the starting temperature.
12. The method of claim 11 , wherein the temperature of the environment is increased to the final temperature at a rate ranging from 0.2° C. per minute to 10° C. per minute.
13. The method of claim 11 , wherein the temperature of the environment is increased to the final temperature at a rate of 2° C. per minute.
14. The method of claim 11 , wherein the starting temperature is ambient temperature and the final temperature ranges from 900° C. to 1500° C.
15. The method of claim 1 , wherein the gaseous atmosphere is provided by N 2 , Ar, or NH 3 .
16. The method of claim 1 , wherein the second heat treatment comprises exposing the co-continuous porous silicon-based material to a temperature ranging from 400° ° C. to 800° C.
17. The method of claim 1 , wherein the co-continuous porous silicon-based material is SiO 2 , SiOC, SiC, or SiCN and pores of the co-continuous porous silicon-based material have an average pore diameter of 100 mm or less.
18. The method of claim 1 , wherein the first heat treatment comprises exposing the co-continuous silicone-based foam material to an environment that has a starting temperature and then increasing the temperature of the environment to a final temperature that is higher than the starting temperature; wherein (i) the temperature of the environment is increased to the final temperature at a rate ranging from 0.2° ° C. per minute to 10° ° C. per minute; (ii) the starting temperature is ambient temperature and the final temperature ranges from 900° C. to 1500° C.; (iii) the second heat treatment comprises exposing the co-continuous porous silicon-based material to a temperature ranging from 400° ° C. to 800° C.; and (iv) the gaseous atmosphere is provided by N 2 or Ar.