Self-healing, omniphobic coatings and related methods

Patent metadata

Field	Value
Publication number	US-12084581-B2
Application number	US-201917261643-A
Country	US
Kind code	B2
Filing date	Aug 16, 2019
Priority date	Aug 16, 2018
Publication date	Sep 10, 2024
Grant date	Sep 10, 2024

Abstract

Self-healable, omniphobic coatings and related methods are provided. In embodiments, a self-healable, omniphobic coating comprises a matrix of crosslinked, entangled hydrogel polymers, the hydrogel polymers comprising hydroxyl (OH) groups, hydroxyl group precursors, or both, and nanoparticles distributed throughout the matrix; and fluorinated silane molecules covalently bound to the matrix.

First claim

What is claimed is:

1. A self-healable, omniphobic coating comprising a matrix of covalently crosslinked, entangled hydrogel polymers, the hydrogel polymers comprising hydroxyl (OH) groups, hydroxyl group precursors, or both, and nanoparticles distributed throughout the matrix; and fluorinated silane molecules covalently bound to the matrix, wherein the matrix's covalent crosslinks are derived from crosslinker molecules comprising glyoxal.

2. The coating of claim 1 , wherein the hydrogel polymers comprise a cellulose ether, an ethylene oxide-based polymer, an epoxidized oil, or combinations thereof.

3. The coating of claim 2 , wherein the hydrogel polymers comprise hydroxypropyl cellulose (HPC), hydroxyethyl cellulose (HEC), hydroxypropyl methylcellulose (HPMC), poly(ethylene glycol) (PEG), poly(ethylene glycol)diacrylate, epoxidized vegetable oil, or combinations thereof.

4. The coating of claim 2 , wherein the hydrogel polymers comprise HPC, HEC, HPMC, or combinations thereof.

5. The coating of claim 1 , wherein the hydrogel polymers do not comprise charged groups when combined with water, the matrix does not comprise a polyelectrolyte, and the coating does not comprise a polyelectrolyte.

6. The coating of claim 1 , wherein the nanoparticles have an average diameter in a range of 5 nm to 50 nm.

7. A self-healable, omniphobic coating comprising a matrix of covalently crosslinked, entangled hydrogel polymers, the hydrogel polymers comprising hydroxyl (OH) groups, hydroxyl group precursors, or both, and nanoparticles distributed throughout the matrix; and fluorinated silane molecules covalently bound to the matrix, wherein the nanoparticles are SiO 2 nanoparticles.

8. A self-healable, omniphobic coating comprising a matrix of covalently crosslinked, entangled hydrogel polymers, the hydrogel polymers comprising hydroxyl (OH) groups, hydroxyl group precursors, or both, and nanoparticles distributed throughout the matrix; and fluorinated silane molecules covalently bound to the matrix, wherein the matrix has a water content in a range of from 1% to 10%, wherein the water content is determined from an equation (M ac −M o )/M ac *100, wherein M ac is the matrix's mass and M o is the mass of the matrix as dried and water-free.

9. The coating of claim 1 , wherein the fluorinated silane molecules are derived from compounds comprising Trichloro(1H,1H,2H,2H-perfluorooctyl)silane, 1H,1H,2H,2H-Perfluorooctyltriethoxysilane, 1H,1H,2H,2H-Perfluorododecyltrichlorosilane, 1H,1H,2H,2H-Perfluorodecyltriethoxysilane, 1H,1H,2H,2H-Perfluorododecyltrichlorosilane, 1H,1H,2H,2H-Perfluorodecyltrimethoxysilane, Diisopropyl(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl)silane, 1H,1H,2H,2H-Perfluorooctyltriethoxysilane, or combinations thereof.

10. A self-healable, omniphobic coating comprising a matrix of covalently crosslinked, entangled hydrogel polymers, the hydrogel polymers comprising hydroxyl (OH) groups, hydroxyl group precursors, or both, and nanoparticles distributed throughout the matrix; and fluorinated silane molecules covalently bound to the matrix, wherein the hydrogel polymers are present at an amount in a range of from 90 wt % to 98 wt %, the nanoparticles are present at an amount in a range of from 1 wt % to 5 wt %, and the coating exhibits a crosslinking density in a range of from 1 mol/cm 3 to 3 mol/cm 3 .

11. The coating of claim 10 , wherein the hydrogel polymers comprise HPC, HEC, HPMC, or combinations thereof, and the nanoparticles are SiO 2 nanoparticles having an average diameter in a range of 5 nm to 50 nm.

12. The coating of claim 11 , wherein the matrix's covalent crosslinks are derived from glyoxal crosslinker molecules.

13. The coating of claim 1 , exhibiting an advancing and a receding contact angle for water and an advancing and a receding contact angle for diiodomethane, each not less than 150°.

14. The coating of claim 1 , the coating disposed on a surface of a substrate.

15. The coating of claim 1 , wherein at a crosslinking density of 1 mol/cm 3 , the coating exhibits a healing efficiency ζ of at least 90% after a 15 μm scratch on the coating is exposed to water vapor of a relative humidity of 100% for 10 s.

16. A method of forming a self-healing, omniphobic surface, the method comprising:
forming the matrix of claim 1 on a surface of a substrate; and
depositing fluorinated silane compounds on a surface of the matrix under conditions to covalently bind the compounds to the matrix to provide the fluorinated silane molecules.

17. The method of claim 16 , wherein the matrix is formed by depositing a matrix solution comprising the hydrogel polymers, crosslinker molecules, the nanoparticles, and a solvent, on the surface of the substrate, followed by evaporating the solvent from the deposited matrix solution.

18. A method of healing a self-healing, omniphobic surface, the method comprising:
exposing the coating of claim 1 to a source of water.

19. The coating of claim 1 , consisting of the covalently crosslinked, entangled hydrogel polymers, covalent crosslinks derived from crosslinker molecules, the nanoparticles, the fluorinated silane molecules, water, and optionally, an initiator.

20. The coating of claim 19 , wherein the hydrogel polymers are selected from HPC, HEC, HPMC, and combinations thereof, the crosslinker molecules are glyoxal molecules, and the nanoparticles are SiO 2 nanoparticles having an average diameter in a range of 5 nm to 50 nm.

21. The coating of claim 20 , wherein the fluorinated silane molecules are 1H,1H,2H,2H-Perfluorododecyltrichlorosilane molecules.

22. A self-healable, omniphobic coating comprising a matrix of covalently crosslinked, entangled hydrogel polymers, the hydrogel polymers comprising hydroxyl (OH) groups, hydroxyl group precursors, or both, and nanoparticles distributed throughout the matrix; and fluorinated silane molecules covalently bound to the matrix, wherein the matrix has a porosity of not more than 60%.

Assignees

• Univ Kansas

Inventors

• Ezazi Mohammadamin
• Maharjan Anjana
• Kwon Gibum

Classifications

• C08K2201/005

  Additives being defined by their particle size in general · CPC title

• C08K5/0025

  Crosslinking or vulcanising agents; including accelerators · CPC title

• B82Y40/00

  Manufacture or treatment of nanostructures · CPC title

• B82Y30/00

  Nanotechnology for materials or surface science, e.g. nanocomposites · CPC title

• B05D5/08

  to obtain an anti-friction or anti-adhesive surface (rendering particulate materials free-flowing in general, e.g. making them hydrophobic B01J2/30) · CPC title