Plunger and methods of producing hydrophobic surfaces

1. A method of forming a hydrophobic coating on at least a portion of a surface comprising the steps:

i) applying a composition comprising water, a polymeric binder that can be diluted with water, and first particles on said at least a portion of a surface, wherein said first particles have a size of about 30 μm to about 225 μm; and

ii) applying second particles having a size of about 1 nm to about 25 μm to said polymeric binder on said at least a portion of said surface; wherein said applying second particles to said polymeric binder comprises applying either a liquid composition comprising said second particles or a spray coating of said second particles, using a stream of gas wherein the second particles comprise less than 2% by weight of a solvent; and

wherein the second particles, or the first particles and second particles, comprise one or more independently selected hydrophobic, or hydrophobic and oleophobic, moieties covalently bound to said first or second particles through a silicon atom independently selected from:

(a) C 6 to 20 alkyl or cycloalkyl, either or both of which are optionally substituted with one or more fluorine atoms, or

(b) —Z—((CF 2 ) q (CF 3 )) r , wherein Z is a C 1 to 12 alkyl group, and where q is an integer from 1 to 12, and r is an integer from 1-4.

2. A method of forming a hydrophobic coating on at least a portion of a surface comprising applying a composition comprising water, a polymeric binder that can be diluted with water, first particles having a size of about 30 μm to about 225 μm, and hydrophobic second particles having a size of about 1 nm to about 25 μm on said at least a portion of a surface,

wherein said second particles, or said first particles and second particles, comprise one or more independently selected hydrophobic, or hydrophobic and oleophobic, moieties covalently bound to said first or second particles through a silicon atom independently selected from:

(a) C 6 to 20 alkyl or cycloalkyl, either or both of which are optionally substituted with one or more fluorine atoms, or

(b) —Z—((CF 2 ) q (CF 3 )) r , wherein Z is a C 1 to 12 alkyl group, and where q is an integer from 1 to 12, and r is an integer from 1-4.

3. A system for preparing a hydrophobic coating comprising as two separate components:

i) a first component comprising water, a polymeric binder that can be diluted with water, and first particles, wherein said first particles have a size from about 30 μm to about 225 μm; and

ii) a second component comprising hydrophobic second particles having a size of about 1 nm to about 25 μm;

wherein said second particles, or said first particles and second particles, comprise one or more independently selected hydrophobic, or hydrophobic and oleophobic, moieties covalently bound to said first or second particles through a silicon atom independently selected from:

(a) C 6 to 20 alkyl or cycloalkyl, either or both of which are optionally substituted with one or more fluorine atoms, or

(b) —Z—((CF 2 ) q (CF 3 )) r , wherein Z is a C 1 to 12 alkyl group, and where q is an integer from 1 to 12, and r is an integer from 1-4.

4. An article having a surface coated with the hydrophobic coating system of claim 3 , wherein said coating has a hydrophobic exposed surface formed by

i) applying the first component comprising the binder on least a portion of the surface; and

ii) applying to the binder on at least a portion of the surface the second component comprising second particles; wherein the resulting coating has a greater amount of second particles on, at, or adjacent to the exposed surface than on, at, or adjacent to the surface of the article.

5. The system of claim 3 , wherein the binder comprises a polyurethane, lacquer, fluoropolymer, or epoxy coating composition.

6. The system of claim 5 , wherein the binder comprises a polyurethane or epoxy coating composition.

7. The system of claim 3 , wherein said second particles, but not said first particles, comprise one or more independently selected hydrophobic, or hydrophobic and oleophobic, moieties covalently bound.

8. The system of claim 3 , wherein said second particles have an average size in a range selected from about 1 nm to about 100 nm, about 100 nm to about 1 micron, about 1.0 micron to about 10 μm, and about 2.5 micron to about 25 μm.

9. The system of claim 3 , wherein said second particles comprise: a metal oxide, an oxide of a metalloid, a silicate, or a glass.

10. A hydrophobic coating prepared by (i) applying the first component of the system of claim 3 to at least a portion of a surface, and (ii) applying the second component of the system of claim 3 to at least a portion of the surface coated by the first component,

wherein the coating is resistant to 40 abrasion cycles on a Taber Model 503 instrument using CS-10 wheels with 250 g load without loss of hydrophobicity.

11. A coating composition comprising: water, a polymeric binder that can be diluted with water, first particles having a size from about 30 μm to about 225 μm, and hydrophobic second particles having a size of about 1 nm to about 25 μm,

wherein said second particles, or said first particles and second particles, comprise one or more independently selected hydrophobic, or hydrophobic and oleophobic, moieties covalently bound to said first or second particles through a silicon atom, wherein said hydrophobic and/or oleophobic moieties are independently selected from:

(a) C 6 to 20 alkyl or cycloalkyl, either or both of which are optionally substituted with one or more fluorine atoms, or

(b) —Z—((CF 2 ) q (CF 3 )) r , wherein Z is a C 1 to 12 alkyl group, and where q is an integer from 1 to 12, and r is an integer from 1-4.

12. The composition of claim 11 , wherein the binder comprises a polyurethane, lacquer, fluoropolymer, or epoxy coating composition.

13. The composition of claim 12 , wherein the binder comprises a polyurethane or epoxy coating composition.

14. The composition of claim 11 , wherein said second particles, but not said first particles, comprise one or more independently selected hydrophobic, or hydrophobic and oleophobic, moieties covalently bound.

15. The composition of claim 14 , wherein said second particles are prepared by treating a particle having a size of about 1 nm to 25 μm with a silanizing agent selected from: tridecafluoro-1,1,2,2-tetrahydrooctyl)silane; (tridecafluoro-1,1,2,2-tetrahydrooctyl) trichlorosilane; (tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane; (tridecafluoro-1,1,2,2-tetrahydrooctyl)trimethoxysilane; (heptadecafluoro-1,1,2,2-tetrahydrodecyl)dimethyl(dimethylamino)silane; (heptadecafluoro-1,1,2,2-tetrahydrodecyl)tris(dimethylamino)silane; n-octadecyltrimethoxysilane; n-octyltriethoxysilane; and nonafluorohexyldimethyl(dimethylamino)silane.

16. The composition of claim 11 , wherein said second particles have an average size in a range selected from about 1 nm to about 100 nm; about 100 nm to about 1 micron; about 1.0 micron to about 10 μm; and about 2.5 micron to about 25 μm.

17. The composition of claim 11 , wherein said second particles comprise: a metal oxide, an oxide of a metalloid, a silicate, or a glass.

18. A hydrophobic coating prepared by applying a composition according to claim 11 to at least a portion of a surface,

wherein said coating is resistant to 40 abrasion cycles on a Taber Model 503 instrument using CS-10 wheels with 250 g load without loss of hydrophobicity.

19. A system for preparing a hydrophobic coating comprising as two separate components:

i) a first component comprising water, a polymeric binder that can be diluted with water, and first particles, wherein said first particles have a size from about 30 μm to about 225 μm; and

ii) a second component comprising hydrophobic second particles having a size of about 1 nm to about 25 μm;

wherein said second particles comprise one or more independently selected fluoroalkyl or perfluoroalkyl moieties covalently bound to the second particles through a silicon atom.

20. The system of claim 19 , wherein said second particles are prepared by treating a particle having a size of about 1 nm to 25 μm with a silanizing agent selected from: tridecafluoro-1,1,2,2-tetrahydrooctyl)silane; (tridecafluoro-1,1,2,2-tetrahydrooctyl) trichlorosilane; (tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane; (tridecafluoro-1,1,2,2-tetrahydrooctyl)trimethoxysilane; (heptadecafluoro-1,1,2,2-tetrahydrodecyl)dimethyl(dimethylamino)silane; (heptadecafluoro-1,1,2,2-tetrahydrodecyl)tris(dimethylamino)silane; n-octadecyltrimethoxysilane; n-octyltriethoxysilane; and nonafluorohexyldimethyl(dimethylamino)silane.

21. The system of claim 19 , wherein said fluoroalkyl or perfluoroalkyl moieties comprise from six to twenty carbon atoms.

22. A system for preparing a hydrophobic coating comprising as two separate components:

i) a first component comprising water, a polymeric binder that can be diluted with water, and first particles, wherein said first particles have a size from about 30 μm to about 225 μm, and wherein said first particles do not comprise a hydrophobic moiety; and

ii) a second component comprising hydrophobic second particles having a size of about 1 nm to about 25 μm;

wherein said second particles comprise one or more independently selected hydrophobic, or hydrophobic and oleophobic, moieties.

23. A coating composition comprising: water, a polymeric binder that can be diluted with water, first particles having a size from about 30 μm to about 225 μm, and hydrophobic second particles having a size of about 1 nm to about 25 μm,

wherein said second particles, or said first particles and second particles, comprise one or more independently selected hydrophobic and/or oleophobic moieties covalently bound to said first or second particles through a silicon atom, wherein said hydrophobic and/or oleophobic moieties are independently selected from:

(a) C 1 to 20 alkyl or cycloalkyl, either or both of which are optionally substituted with one or more fluorine atoms, or

(b) —Z—((CF 2 ) q (CF 3 )) r , wherein Z is a C 1 to 12 alkyl group, and where q is an integer from 1 to 12, and r is an integer from 1-4; and

wherein said first particles are hollow microspheres.

24. The composition of claim 23 , wherein said first particles are hollow microspheres that have an average diameter greater than about 30 μm and less than about 200 μm.

25. The composition of claim 23 , wherein said second particles are prepared by treating a particle having a size of about 1 nm to about 25 μm with a silanizing agent selected from: dimethyldichlorosilane, octyltrimethoxysilane, or tridecafluoro-1,1,2,2-tetrahydrooctyl trichlorosilane.

26. A coating composition comprising: water, a polymeric binder that can be diluted with water, first particles having a size from about 30 μm to about 225 μm, and hydrophobic second particles having a size of about 1 nm to about 25 μm,

wherein said second particles, or said first particles and second particles, comprise one or more independently selected hydrophobic and/or oleophobic moieties covalently bound to said first or second particles through a silicon atom, wherein said hydrophobic and/or oleophobic moieties are independently selected from:

(a) C 1 to 20 alkyl or cycloalkyl, either or both of which are optionally substituted with one or more fluorine atoms, or

(b) —Z—((CF 2 ) q (CF 3 )) r , wherein Z is a C 1 to 12 alkyl group, and where q is an integer from 1 to 12, and r is an integer from 1-4; and

wherein said one or more hydrophobic, or hydrophobic and oleophobic, moieties comprise one or more independently selected fluoroalkyl or perfluoroalkyl moieties.

27. A coating composition for preparing a hydrophobic coating comprising: water, a polymeric binder that can be diluted with water, first particles having a size from about 30 μm to about 225 μm, and hydrophobic second particles having a size of about 1 nm to about 25 μm,

wherein said first particles do not comprise a hydrophobic moiety wherein, upon curing the coating formed from the coating composition is hydrophobic with a contact angle greater than 90° with water at 23° C., and

wherein the second particles comprise one or more independently selected hydrophobic moieties covalently bound to said first or second particles through a silicon atom independently selected from:

(a) C 6 to 20 alkyl or cycloalkyl, either or both of which are optionally substituted with one or more fluorine atoms, or

(b) —Z—((CF 2 ) q (CF 3 )) r , wherein Z is a C 1 to 12 alkyl group, and where q is an integer from 1 to 12, and r is an integer from 1-4.

28. The composition of claim 27 , wherein upon curing the coating formed from the coating composition is resistant to 60 abrasion cycles on a Taber Model: 503 instrument using CS-10 wheels with 250 g load without loss of hydrophobicity.