Barrier coatings for polymeric substrates

• US 9,403,992 B2
• Filed: 11/13/2013
• Issued: 08/02/2016
• Est. Priority Date: 02/28/2007
• Status: Active Grant

• Current Assignee: The Boeing Co.
• Original Assignee: The Boeing Co.
• Inventors: Larson-Smith, Kjersta L., Pare, Shawn M., Sundaram, Vasan S.
• Primary Examiner(s): Heincer, Liam J
• Application Number:
  US14/078,615
• Publication Number:
  US 20140065395A1
• Time in Patent Office: 993 Days
• US Class Current: 1/1
• CPC Class Codes: B05D 1/62 Plasma-deposition of organic layers plasma deposition in general C23C14/00, C23C16/00
• CPC Class Codes: B05D 7/04 to surfaces of films or sheets producing layered products by applying coatings of pasty or pulverulent plastics B29C41/00
• CPC Class Codes: B05D 7/57 the last layer being a clear coat
• CPC Class Codes: B64C 1/1484 Windows B64C1/1492 takes precedence
• CPC Class Codes: B64F 5/60 Testing or inspecting aircraft components or systems
• CPC Class Codes: C08J 2333/06 of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
• CPC Class Codes: C08J 2369/00 Characterised by the use of polycarbonates; Derivatives of polycarbonates
• CPC Class Codes: C08J 2483/04 Polysiloxanes
• CPC Class Codes: C08J 7/0423 with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
• CPC Class Codes: C08J 7/043 Improving the adhesiveness of the coatings per se, e.g. forming primers adhesives in the form of films or foils characterised by the primer layers between the polymer carriers and the adhesives C09J7/50
• CPC Class Codes: C08J 7/044 Forming conductive coatings; Forming coatings having anti-static properties
• CPC Class Codes: C08J 7/046 Forming abrasion-resistant coatings; Forming surface-hardening coatings
• CPC Class Codes: C09D 5/00 Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced electrically insulating plastics, resins or waxes H01B3/30; Filling pastes
• CPC Class Codes: Y10T 428/24802 Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
• CPC Class Codes: Y10T 428/24851 Intermediate layer is discontinuous or differential
• CPC Class Codes: Y10T 428/24917 including metal layer
• CPC Class Codes: Y10T 428/24975 No layer or component greater than 5 mils thick
• CPC Class Codes: Y10T 428/24983 Hardness
• CPC Class Codes: Y10T 428/265 1 mil or less
• CPC Class Codes: Y10T 428/31504 Composite [nonstructural laminate]
• CPC Class Codes: Y10T 428/31507 : Of polycarbonate
• CPC Class Codes: Y10T 428/31663 : As siloxane, silicone or silane
• CPC Class Codes: Y10T 428/31935 : Ester, halide or nitrile of addition polymer

Abstract

An exemplary embodiment provides coated polymeric substrates that have a polymeric substrate body with a coated surface. The surface coating includes more than one pair of coating layers. Each pair of coating layers includes a first applied coating layer and a second applied coating layer. In addition, an indicator, applied on top of or between coating layers, provides an indication of wear of the coating. The first and second applied coating layers have a thickness between about 3 to about 10 nanometers. The coating exhibits a Hall-Petch effect.

Claims

1. A coated polymeric substrate comprising:

a polymeric substrate having a first surface;

a coating on the first surface, the coating comprising;

at least one pair of coating layers comprising a first applied coating layer and a second applied coating layer;

wherein the first and second applied coating layers have a thickness between about 3 to about 10 nanometers and the second applied coating layer comprising SiO_XC_y where x ranges from 1.0 to 1.2 and y ranges from 1.0 to 0.8;

wherein the coating exhibits a Hall-Petch effect.

2. The substrate of claim 1, wherein the coating includes more than one pair of coating layers, each pair comprising a first applied coating layer and a second applied coating layer.

3. The substrate of claim 1, wherein the first applied coating layer is deposited by a plasma enhanced chemical vapor deposition-applied coating layer or an electron beam deposited coating layer, the second applied coating layer harder than the first applied coating layer.

4. The substrate of claim 1, wherein the second applied coating layer comprises a plasma enhanced chemical vapor deposition-applied coating layer or an electron beam deposited coating layer or ion assisted deposition layer, the second applied coating layer harder than the first applied coating layer.

5. The substrate of claim 1, wherein the polymeric substrate body and the coating are both optically transparent in light of a wavelength region of human vision.

6. The substrate of claim 1, wherein the coating on the first surface of the polymeric substrate, when subjected to a wiper abrasion durability test in accordance with D6-82942-1, suffers a haze change of not more than about 1% after 155,000 cycles.

7. The substrate of claim 1, wherein the coating on the first surface of the polymeric substrate, when subjected to a Taber Wear Test in accordance with ASTM 1044-05, suffers a haze change of not more than about 5% after 40,000 cycles.

8. The substrate of claim 1, wherein the coating on the first surface of the polymeric substrate, when subjected to a sand erosion test in accordance with ASTM D968-93, suffers a haze change of not more than about 15%, using about 5 liters of sand of mean size 800.

9. The substrate of claim 1, wherein the coating on the first surface of the polymeric substrate, when subjected to a flex test in accordance with ASTM D-790, showed no cracking or crazing after 500 cycles.

10. The substrate of claim 1, wherein the polymeric substrate body comprises an aircraft windshield.

11. The substrate of claim 1, wherein the polymeric substrate body comprises acrylic or polycarbonate.

12. The substrate of claim 1, wherein the polymeric substrate body comprises stretched acrylic.

13. The substrate of claim 1, further comprising an indicator applied on top of or between coating layers, the indicator providing indicia of wear of the coating.

14. The substrate of claim 13, wherein the indicator comprises a metallic coating layer or a hydrophobic coating layer.

15. A polymeric substrate comprising:

a polymeric substrate body configured in a size and shape of an aircraft windshield, the polymeric substrate body having a first surface corresponding to an outer surface of the aircraft windshield;

a coating on the first surface, the coating comprising;

at least one pair of coating layers comprising a first applied coating layer and a second applied coating layer; and

an indicator applied on top of or between coating layers, the indicator providing indicia of wear of the coating;

wherein the first and second applied coating layers have a thickness between about 3 to about 10 nanometers and the second applied coating layer comprises SiO_XC_Y where x ranges from 1.0 to 1.2 and y ranges from 1.0 to 0.8;

where the coating exhibits a Hall-Petch effect.

16. The polymeric substrate of claim 15, wherein more than one pair of coating layers, each pair comprising a first applied coating layer and a second applied coating layer.

17. The polymeric substrate of claim 15, wherein, after exposure of the coating to chemicals selected from dc-icing fluid, jet fuel, methyl ethyl ketone, solvent cleaner, alkaline cleaner, hydraulic fluid, and detergent, testing in accordance with a Taber Wear Test ASTM D-1044-99 for 100 cycles results in a change in haze of not more than about 1%.

18. The substrate of claim 15, wherein the first applied coating layer is deposited by a plasma enhanced chemical vapor deposition-applied coating layer or an electron beam deposited coating layer, the second applied coating layer harder than the first applied coating layer.

19. The substrate of claim 15, wherein the second applied coating layer comprises a plasma enhanced chemical vapor deposition-applied coating layer or an electron beam deposited coating layer or ion assisted deposition layer, the second applied coating layer harder than the first applied coating layer.

20. The substrate of claim 15, wherein the coating, when subjected to a wiper abrasion durability test in accordance with D6-82942-1, suffers a haze change of not more than about 1% after 155,000 cycles.

21. The substrate of claim 15, wherein the coating, when subjected to a sand erosion test in accordance with ASTM D968-93, suffers a haze change of not more than about 15%, using about 5 liters of sand of mean size 800 microns.

22. The substrate of claim 15, wherein the coating on the first surface of the polymeric substrate, when subjected to a flex test in accordance with ASTM D-790, showed no cracking or crazing after 500 cycles.