Abrasion wear resistant coated substrate product

• US 5,637,353 A
• Filed: 01/18/1996
• Issued: 06/10/1997
• Est. Priority Date: 09/27/1990
• Status: Expired due to Term

• Current Assignee: Morgan Chemical Products, Inc.
• Original Assignee: Monsanto Company (Bayer AG)
• Inventors: Finke, Steven J., Kimock, Fred M., Knapp, Bradley J., Galdieri, John V.
• Primary Examiner(s): TURNER, ARCHENE A
• Application Number:
  US08/588,109
• Time in Patent Office: 509 Days
• Field of Search: 427/248.1, 427/249, 427/255, 427/255.1, 427/255.2, 427/255.7, 427/309
• US Class Current: 427/255.34
• CPC Class Codes: B32B 17/06 comprising glass as the main or only constituent of a layer, next to another layer of a specific material
• CPC Class Codes: C03C 17/06 with metals C03C17/34, C03C17/44 take precedence
• CPC Class Codes: C03C 17/3417 all coatings being oxide coatings
• CPC Class Codes: C03C 17/3435 comprising a nitride, oxynitride, boronitride or carbonitride
• CPC Class Codes: C03C 17/3441 comprising carbon, a carbide or oxycarbide
• CPC Class Codes: C03C 17/3452 comprising a fluoride
• CPC Class Codes: C03C 17/347 comprising a sulfide or oxysulfide
• CPC Class Codes: C03C 17/3476 comprising a selenide or telluride
• CPC Class Codes: C03C 17/36 at least one coating being a metal
• CPC Class Codes: C03C 17/3613 Coatings of type glass/inorganic compound/metal/inorganic compound/metal/other
• CPC Class Codes: C03C 17/3618 Coatings of type glass/inorganic compound/other inorganic layers, at least one layer being metallic
• CPC Class Codes: C03C 17/3621 one layer at least containing a fluoride
• CPC Class Codes: C03C 17/3626 one layer at least containing a nitride, oxynitride, boronitride or carbonitride
• CPC Class Codes: C03C 17/3628 one layer at least containing a sulfide
• CPC Class Codes: C03C 17/3634 one layer at least containing carbon, a carbide or oxycarbide
• CPC Class Codes: C03C 17/3642 the multilayer coating containing a metal layer
• CPC Class Codes: C03C 2217/734 comprising an alternation of high and low refractive indexes
• CPC Class Codes: C03C 2217/78 Coatings specially designed to be durable, e.g. scratch-resistant
• CPC Class Codes: C03C 2218/31 Pre-treatment
• CPC Class Codes: C03C 23/005 by atoms
• CPC Class Codes: C23C 14/021 : Cleaning or etching treatments
• CPC Class Codes: C23C 14/024 : Deposition of sublayers, e.g. to promote adhesion of the coating C23C14/027 takes precedence
• CPC Class Codes: C23C 14/025 : Metallic sublayers
• CPC Class Codes: C23C 14/06 : characterised by the coating material C23C14/0021 , C23C14/04 take precedence
• CPC Class Codes: C23C 14/0605 : Carbon
• CPC Class Codes: C23C 14/0647 : Boron nitride
• CPC Class Codes: C23C 14/0676 : Oxynitrides
• CPC Class Codes: C23C 14/081 : of aluminium, magnesium or beryllium
• CPC Class Codes: C23C 14/083 : of refractory metals or yttrium
• CPC Class Codes: C23C 14/086 : of zinc, germanium, cadmium, indium, tin, thallium or bismuth
• CPC Class Codes: C23C 16/0227 : by cleaning or etching
• CPC Class Codes: C23C 16/0272 : Deposition of sub-layers, e.g. to promote the adhesion of the main coating
• CPC Class Codes: C23C 16/0281 : of metallic sub-layers C23C16/029 takes precedence
• CPC Class Codes: C23C 16/26 : Deposition of carbon only
• CPC Class Codes: G02B 1/105 : Protective coatings
• CPC Class Codes: G02B 1/14 : Protective coatings, e.g. hard coatings
• CPC Class Codes: Y10S 427/103 : Diamond-like carbon coating, i.e. DLC
• CPC Class Codes: Y10T 428/24975 : No layer or component greater than 5 mils thick

Abstract

The coated substrate product finds particular application in eyeglass and sunglass lenses, architectural glass, analytical instrument windows, automotive windshields and laser bar code scanners for use in retail stores and supermarkets. The product has greatly improved wear resistance for severe abrasive environments and comprises a substantially optically transparent substrate, one or more chemically vapor deposited interlayers bonded to the substrate and a chemically vapor deposited outer layer of optically transparent or substantially optically transparent hard and low friction material bonded to the interlayer and away from the substrate.

Claims

1. A chemical vapor deposition method for producing an abrasion wear resistant coated substrate product comprising:

chemically de-greasing the surface of a parent substrate which is substantially optically transparent to light in the visible region of 350 to approximately 750 nanometers and which comprises a material selected from the group consisting of an amorphous material, a single crystal, polycrystalline materials, glass, salt materials, ceramic materials and mixtures thereof to remove hydrocarbon contamination;

placing said substrate into a chemical vapor deposition reactor vacuum chamber and evacuating the air from said chamber;

sputter-etching the surface of said substrate with energetic gas ions to remove traces of residual hydrocarbon and to preferentially reduce the concentration of alkali metal atoms and alkali metal oxides at the substrate surface;

chemically vapor depositing onto said substrate a composite layer comprising at least one interlayer which is substantially optically transparent to light in the visible region of 350 to approximately 750 nanometers, has a thickness in the range of about 1 μ

m to about 20 μ

m and has a hardness greater than the hardness of said substrate;

chemically vapor depositing onto said coated substrate an outer layer of optically transparent, hard and low friction material which is transparent to light in the visible region of 350 to approximately 750 nanometers and is bonded to said composite layer and away from said substrate;

cooling said coated substrate by extinguishing said deposition process and passing an inert gas over said substrate until the temperature of said substrate has reached substantially room temperature during said cool-down step; and

recovering a coated substrate product exhibiting greatly improved wear resistance for severe abrasive environments.

2. The method of claim 1 wherein said outer layer is selected from the group consisting of tin oxide, indium oxide, aluminum oxide, zirconium oxide, boron nitride, boron carbide, molybdenum disulfide, carbon nitride, mixtures thereof and chemically bonded combinations thereof.

3. The method of claim 1 wherein said composite layer is selected from the group consisting of silicon nitride, titanium nitride, tantalum nitride, hafnium nitride, zirconium nitride, boron nitride, yttrium oxide, germanium oxide, silicon dioxide, tantalum oxide, titanium oxide, zirconium oxide, hafnium oxide, silicon oxide, silicon carbide, germanium carbide, aluminum oxide, aluminum nitride, cerium oxide, tin oxide, indium oxide, thorium oxide, lithium oxide, sodium oxide, potassium oxide, rubidium oxide, cesium oxide, francium oxide, beryllium oxide, magnesium oxide, calcium oxide, strontium oxide, cerium oxide, radium oxide, barium fluoride, cerium fluoride, magnesium fluoride, thorium fluoride, calcium fluoride, neodymium fluoride, lead fluoride, sodium fluoride, lithium fluoride, zinc selenide, zinc sulfide, mixtures thereof and chemically bonded combinations thereof.

4. The method of claim 1 wherein the thickness of said outer layer is at least 50 Å

thick.

5. The method of claim 1 wherein said composite layer comprises at least one additional interlayer having a thickness in the range of about 10 Å

to about 1 μ

m.

6. The method of claim 5 wherein said additional interlayer is selected from the group consisting of silicon nitride, titanium nitride, tantalum nitride, hafnium nitride, zirconium nitride, boron nitride, yttrium oxide, germanium oxide, silicon dioxide, tantalum oxide, titanium oxide, zirconium oxide, hafnium oxide, silicon oxide, silicon carbide, germanium carbide, aluminum oxide, aluminum nitride, cerium oxide, tin oxide, indium oxide, thorium oxide, lithium oxide, sodium oxide, potassium oxide, rubidium oxide, cesium oxide, francium oxide, beryllium oxide, magnesium oxide, calcium oxide, strontium oxide, cerium oxide, radium oxide, barium fluoride, cerium fluoride, magnesium fluoride, thorium fluoride, calcium fluoride, neodymium fluoride, lead fluoride, sodium fluoride, lithium fluoride, zinc selenide, zinc sulfide, mixtures thereof and chemically bonded combinations thereof.

7. The method of claim 1 wherein said composite layer includes at least one metallic interlayer having a thickness in the range of about 10 Å

to about 1000 Å

.

8. The method of claim 7 wherein said metallic interlayer is selected from the group consisting of silicon, germanium, hafnium, molybdenum, tungsten, yttrium, tantalum, titanium, zirconium, vanadium, niobium, chromium, manganese, rhenium, technetium, iron, cobalt, iridium, rhodium, nickel, palladium, platinum, copper, silver, gold, zinc, ruthenium, indium, aluminum, tin, osmium, thallium, lead, antimony, bismuth, polonium, and mixtures thereof.

9. A chemical vapor deposition method for producing an abrasion wear resistant coated substrate product comprising:

chemically de-greasing the surface of a parent substrate which is substantially optically transparent to light in the visible region of 350 to approximately 750 nanometers and which comprises a material selected from the group consisting of an amorphous material, a single crystal, polycrystalline materials, glass, salt materials, ceramic materials and mixtures thereof to remove hydrocarbon contamination;

placing said substrate into a chemical vapor deposition reactor vacuum chamber and evacuating the air from said chamber;

sputter-etching the surface of said substrate with energetic gas ions to remove traces of residual hydrocarbon and to preferentially reduce the concentration of alkali metal atoms and alkali metal oxides at the substrate surface;

chemically vapor depositing onto said substrate a composite layer comprising at least one interlayer which is substantially optically transparent to light in the visible region of 350 to approximately 750 nanometers, has a thickness in the range of about 1 μ

m to about 20 μ

m, has a hardness greater than the hardness of said substrate, and is selected from the group consisting of silicon nitride, zirconium nitride, boron nitride, yttrium oxide, silicon oxide, silicon dioxide, zirconium oxide, silicon carbide, aluminum oxide, aluminum nitride, mixtures thereof and chemically combinations thereof;

chemically vapor depositing onto said coated substrate an outer layer of substantially optically transparent, hard and low friction material which is transparent to light in the visible region of 350 to approximately 750 nanometers, is bonded to said composite layer and away from said substrate and is selected from the group consisting of tin oxide, indium oxide, aluminum oxide, zirconium oxide, boron nitride, boron carbide, molybdenum disulfide, carbon nitride, mixtures thereof and chemically bonded combinations thereof;

cooling said coated substrate by extinguishing said deposition process and passing an inert gas over said substrate until the temperature of said substrate has reached substantially room temperature during said cool-down step; and

recovering a coated substrate product exhibiting greatly improved wear resistance for severe abrasive environments.

10. The method of claim 9 wherein the thickness of said outer layer is at least 50 Å

thick.

11. The method of claim 9 wherein said composite layer comprises at least one additional interlayer having a thickness in the range of about 10 Å

to about 1 μ

m.

12. The method of claim 11 wherein said additional interlayer is selected from the group consisting of silicon nitride, titanium nitride, tantalum nitride, hafnium nitride, zirconium nitride, boron nitride, yttrium oxide, germanium oxide, silicon dioxide, tantalum oxide, titanium oxide, zirconium oxide, hafnium oxide, silicon oxide, silicon carbide, germanium carbide, aluminum oxide, aluminum nitride, cerium oxide, tin oxide, indium oxide, thorium oxide, lithium oxide, sodium oxide, potassium oxide, rubidium oxide, cesium oxide, francium oxide, beryllium oxide, magnesium oxide, calcium oxide, strontium oxide, cerium oxide, radium oxide, barium fluoride, cerium fluoride, magnesium fluoride, thorium fluoride, calcium fluoride, neodymium fluoride, lead fluoride, sodium fluoride, lithium fluoride, zinc selenide, zinc sulfide, mixtures thereof and chemically bonded combinations thereof.

13. The method of claim 9 wherein said composite layer includes at least one metallic interlayer having a thickness in the range of about 10 Å

to about 1000 Å

.

14. The method of claim 13 wherein said metallic interlayer is selected from the group consisting of silicon, germanium, hafnium, molybdenum, tungsten, yttrium, tantalum, titanium, zirconium, vanadium, niobium, chromium, manganese, rhenium, technetium, iron, cobalt, iridium, rhodium, nickel, palladium, platinum, copper, silver, gold, zinc, ruthenium, indium, aluminum, tin, osmium, thallium, lead, antimony, bismuth, polonium, and mixtures thereof.

15. A chemical vapor deposition method for producing an abrasion wear resistant coated substrate product comprising:

chemically de-greasing the surface of a glass substrate which is substantially optically transparent to light in the visible region of 350 to approximately 750 nanometers to remove hydrocarbon contamination;

placing said substrate into a chemical vapor deposition reactor vacuum chamber and evacuating the air from said chamber;

sputter-etching the surface of said substrate with energetic gas ions to remove traces of residual hydrocarbon and to preferentially reduce the concentration of alkali metal atoms and alkali metal oxides at the substrate surface;

chemically vapor depositing onto said substrate a composite layer comprising at least one interlayer of silicon oxy-nitride which is substantially optically transparent to light in the visible region of 350 to approximately 750 nanometers and has a thickness in the range of about 1 μ

m to about 20 μ

m;

chemically vapor depositing onto said coated substrate an outer layer of substantially optically transparent, hard and low friction material which is transparent to light in the visible region of 350 to approximately 750 nanometers, is bonded to said composite layer and away from said substrate and is selected from the group consisting of tin oxide, indium oxide, aluminum oxide, zirconium oxide, boron nitride, boron carbide, molybdenum disulfide, carbon nitride, mixtures thereof and chemically bonded combinations thereof;

cooling said coated substrate by extinguishing said deposition process and passing an inert gas over said substrate until the temperature of said substrate has reached substantially room temperature during said cool-down step; and

recovering a coated substrate product exhibiting greatly improved wear resistance for severe abrasive environments.

16. The method of claim 15 wherein the thickness of said outer layer is at least 50 Å

thick.

17. The method of claim 15 wherein said composite layer comprises at least one additional interlayer having a thickness in the range of about 10 Å

to about 1 μ

m.

18. The method of claim 17 wherein said additional interlayer is selected from the group consisting of silicon nitride, titanium nitride, tantalum nitride, hafnium nitride, zirconium nitride, boron nitride, yttrium oxide, germanium oxide, silicon dioxide, tantalum oxide, titanium oxide, zirconium oxide, hafnium oxide, silicon oxide, silicon carbide, germanium carbide, aluminum oxide, aluminum nitride, cerium oxide, tin oxide, indium oxide, thorium oxide, lithium oxide, sodium oxide, potassium oxide, rubidium oxide, cesium oxide, francium oxide, beryllium oxide, magnesium oxide, calcium oxide, strontium oxide, cerium oxide, radium oxide, barium fluoride, cerium fluoride, magnesium fluoride, thorium fluoride, calcium fluoride, neodymium fluoride, lead fluoride, sodium fluoride, lithium fluoride, zinc selenide, zinc sulfide, mixtures thereof and chemically bonded combinations thereof.

19. The method of claim 15 wherein said composite layer includes at least one metallic interlayer having a thickness in the range of about 10 Å

to about 1000 Å

.

20. The method of claim 19 wherein said metallic interlayer is selected from the group consisting of silicon, germanium, hafnium, molybdenum, tungsten, yttrium, tantalum, titanium, zirconium, vanadium, niobium, chromium, manganese, rhenium, technetium, iron, cobalt, iridium, rhodium, nickel, palladium, platinum, copper, silver, gold, zinc, ruthenium, indium, aluminum, tin, osmium, thallium, lead, antimony, bismuth, polonium, and mixtures thereof.

21. The method of claim 17 wherein the product is a bar code scanner window.