Hydrophobic coating including DLC on substrate

• US 6,335,086 B1
• Filed: 06/01/2000
• Issued: 01/01/2002
• Est. Priority Date: 05/03/1999
• Status: Expired due to Term

• Current Assignee: Guardian Glass LLC (KOCH Industries Incorporated)
• Original Assignee: Guardian Industries Corporation (KOCH Industries Incorporated)
• Inventors: Veerasamy, Vijayen S.
• Primary Examiner(s): TURNER, ARCHENE A
• Application Number:
  US09/583,862
• Time in Patent Office: 579 Days
• Field of Search: 428/428, 428/426, 428/408, 428/446, 428/212, 428/217
• US Class Current: 428/217
• CPC Class Codes: B05D 5/083 involving the use of fluoropolymers
• CPC Class Codes: B08B 17/06 by giving articles subject to fouling a special shape or arrangement
• CPC Class Codes: B08B 17/065 the surface having a microscopic surface pattern to achieve the same effect as a lotus flower
• CPC Class Codes: B32B 17/10018 comprising only one glass sheet
• CPC Class Codes: B32B 17/1033 Laminated safety glass or glazing containing temporary protective coatings or layers
• CPC Class Codes: B32B 17/10577 Surface roughness
• CPC Class Codes: B60S 1/54 using gas, e.g. hot air
• CPC Class Codes: B60S 1/58 for rear windows
• CPC Class Codes: B62D 35/007 Rear spoilers B62D35/001 takes precedence
• CPC Class Codes: C03C 17/22 with other inorganic material C03C17/34, C03C17/44 take precedence
• CPC Class Codes: C03C 17/3441 comprising carbon, a carbide or oxycarbide
• CPC Class Codes: C03C 17/3482 comprising silicon, hydrogenated silicon or a silicide
• CPC Class Codes: C03C 17/36 at least one coating being a metal
• CPC Class Codes: C03C 17/3634 one layer at least containing carbon, a carbide or oxycarbide
• CPC Class Codes: C03C 17/3644 the metal being silver
• CPC Class Codes: C03C 17/3652 the coating stack containing at least one sacrificial layer to protect the metal from oxidation
• CPC Class Codes: C03C 2217/282 Carbides, silicides
• CPC Class Codes: C03C 2217/76 Hydrophobic and oleophobic coatings
• CPC Class Codes: C03C 2217/78 Coatings specially designed to be durable, e.g. scratch-resistant
• CPC Class Codes: C03C 2218/151 by vacuum evaporation
• CPC Class Codes: C03C 2218/31 : Pre-treatment
• CPC Class Codes: C03C 23/0075 : Cleaning of glass specially adapted to plate glass B08B11/00
• CPC Class Codes: C03C 3/076 : with 40% to 90% silica, by weight C03C3/045 takes precedence
• CPC Class Codes: Y02T 10/82 : Elements for improving aerodynamics
• CPC Class Codes: Y10T 428/24942 : including components having same physical characteristic in differing degree
• CPC Class Codes: Y10T 428/24983 : Hardness
• CPC Class Codes: Y10T 428/30 : Self-sustaining carbon mass or layer with impregnant or other layer

Abstract

A substrate is coated with a hydrophobic coating system including highly tetrahedral amorphous carbon that is a form of diamond-like carbon (DLC). In certain embodiments, the coating system is deposited on the substrate in a manner to increase its hydrophobicity. In certain embodiments, the coating system is deposited in a manner such that it has an average hardness of at least about 10 GPa, more preferably from about 20-80 GPa. In certain embodiments, the coating system includes first and second DLC inclusive layers that are deposited using one or more ion beam deposition devices, wherein different gases are used to deposit the respective DLC inclusive layers such that the overlying layer has greater scratch resistance characteristics than the underlying layer which functions as an anchoring layer.

Claims

1. A coated glass article comprising:

a glass substrate comprising, on a weight basis;

SiO₂ from about 60-80%,

Na₂O from about 10-20%,

CaO from about 0-16%,

K₂O from about 0-10%,

MgO from about 0-10%,

Al₂O₃ from about 0-5%;

a hydrophobic coating system including diamond-like carbon (DLC) and sp³ carbon-carbon bonds provided on said glass substrate;

said hydrophobic coating system including first and second DLC inclusive layers, said first layer including silicon (Si) and being provided between said second layer and said substrate;

wherein said second layer is deposited in a manner so that said second layer has a higher hardness and higher density than said first layer; and

wherein said hydrophobic coating system has an initial contact angle θ

with a sessile drop of water thereon of at least about 80 degrees, and an average hardness of at least about 10 GPa.

2. The coated glass article of claim 1, wherein said initial contact angle is at least about 100 degrees.

3. The coated glass article of claim 2, wherein said initial contact angle is at least about 110 degrees.

4. The coated glass article of claim 2, wherein said initial contact angle is at least about 125 degrees.

5. The coated glass article of claim 1, wherein said coating system has a surface energy γ

_C of less than or equal to about 20.2 mN/m.

6. The coated glass article of claim 1, wherein said coating system has a surface energy γ

_C of less than or equal to about 19.5 mN/m.

7. The coated glass article of claim 1, wherein said coating system has a surface energy γ

_C of less than or equal to about 18.0 mN/m, and wherein a refractive index “

n”

of said first layer is from about 1.5 to 1.7.

8. The coated glass article of claim 1, wherein said first layer is in direct contact with said glass substrate.

9. The coated glass article of claim 1, further comprising an intermediate layer disposed between said coating system and said glass substrate.

10. The coated glass article of claim 1, further comprising a low-E or IR-reflective layer system disposed between said coating system and said glass substrate.

11. The coated glass article of claim 1, wherein said glass substrate is a soda lime silica glass substrate including from about 66-75% SiO₂, from about 10-20% Na₂O, from about 5-15% CaO, from about 0-5% MgO, from about 0-5% Al₂O₃, and from about 0-5% K₂O.

12. The coated glass article of claim 1, wherein said hydrophobic coating system has an average hardness of at least about 20 GPa.

13. The coated glass article of claim 1, wherein said first layer is deposited using a first gas including silicon (Si) in an ion beam source and said second layer is deposited using a second gas different than said first gas.

14. The coated glass of claim 1, wherein each of said first and second layers comprises silicon (Si), and wherein said first layer comprises more silicon (Si) than said second layer.

15. The coated glass article of claim 1, wherein the coated glass article comprises the following characteristics:

visible transmittance (Ill. A);

>

60%

UV transmittance;

<

38%

IR transmittance;

<

35%.

16. The coated glass article of claim 1, wherein each of said first and second layers include sp³ carbon-carbon bonds.

17. The coated glass article of claim 1, wherein at least about 50% of carbon-carbon bonds in said second layer are sp³ carbon-carbon bonds.

18. A coated article comprising:

a substrate;

a coating system including first and second diamond-like carbon (DLC) inclusive layers provided on said substrate, said first layer further including silicon (Si); and

wherein said coating system has an initial contact angle θ

with a drop of water of at least about 80 degrees, and an average hardness of at least about 10 GPa.

19. The coated article of claim 18, wherein said initial contact angle is at least about 100 degrees, and wherein said first layer includes more Si than said second layer, and said first layer is located at least partially between said substrate and said second layer.

20. The coated article of claim 18, wherein said substrate comprises at least one of glass, ceramic, and plastic;

and wherein a cross sectional thickness of said first layer includes at least about five (5) times as many silicon (Si) atoms as a cross sectional thickness of said second layer.

21. The coated article of claim 18, wherein said coating system is one of:

(i) in direct contact with said substrate, and (ii) on said glass substrate in a manner such that at least one intermediate layer is disposed between said substrate and said coating system.

22. The coated article of claim 18, wherein said coating system has an average hardness of from about 20-80 GPa.

23. The coated article of claim 18, wherein the substrate is glass and the coated article comprises the following characteristics:

visible transmittance (Ill. A);

>

60%

UV transmittance;

<

38%

IR transmittance;

<

35%.

24. The coated article of claim 18, wherein at least about 50% of carbon-carbon bonds in said second layer are sp³ carbon-carbon bonds, and wherein said first layer also comprises sp³ carbon-carbon bonds.

25. The coated article of claim 18, wherein an outermost 10 angstrom layer portion of said second layer includes in atomic percentage:

from about 5-60% carbon (C), from about 0-40% oxygen (O), from about 0-40% silicon (Si), from about 10-95% hydrogen (H), and from about 0-10% fluorine (F).

26. A coated article comprising:

a substrate;

a coating system including at least one diamond-like carbon (DLC) inclusive layer provided on said substrate; and

wherein said coating system has an initial contact angle θ

with a drop of water of at least about 80 degrees, an initial tilt angle β

of no greater than about 30 degrees, and an average hardness of at least about 10 GPa.

27. The coated article of claim 26, wherein said coating system has an initial contact angle θ

with a drop of water of at least about 100 degrees, and an initial tilt angle β

of no greater than about 20 degrees.

28. The coated article of claim 27, wherein said coating system has an initial tilt angle β

of no greater than about 10 degrees.

29. The coated article of claim 26, wherein said coating system includes first and second diamond-like carbon inclusive layers deposited using different gases, respectively, so that said first layer includes more Si than said second layer;

wherein said first layer is located between said second layer and said substrate; and

wherein said second layer has a greater hardness and a greater density than said first layer.

30. The coated article of claim 26, wherein said coating system includes first and second DLC inclusive layers;

and wherein a cross section of said first DLC inclusive layer includes at least about five (5) times as much Si as a cross sectional thickness of said second DLC inclusive layer.

31. The coated article of claim 30, wherein a cross sectional thickness of said first layer includes at least about two (2) times as many O atoms as a cross sectional thickness of said second layer.

32. The coated article of claim 31, wherein a cross sectional thickness of said first layer includes substantially less C atoms than a cross sectional thickness of said second layer.

33. A coated article comprising:

a substrate;

a coating system including a diamond-like carbon (DLC) inclusive portion having at least one layer provided on said substrate; and

wherein an amount of carbon, C, progressively increases through a substantial portion of a thickness of the DLC inclusive portion toward an exterior surface of the coating system.

34. The article of claim 33, wherein an amount of Si progressively decreases through the substantial portion of the thickness of the DLC inclusive portion toward the exterior surface of the coating system.

35. The article of claim 33, wherein an amount of oxygen (O) progressively decreases through the substantial portion of the thickness of the DLC inclusive portion toward the exterior surface of the coating system.

36. The article of claim 33, wherein said coating system has an initial contact angle θ

with a drop of water of at least about 80 degrees, and an average hardness of at least about 10 GPa.