Energetically bonded aluminum and oleophobic / hydrophobic coatings for substrate

Abstract

To provide optical-quality mirrors having an energetically bonded oleophobic / hydrophobic (O / H) coating, and methods of manufacturing and using such coatings and mirrors.SOLUTION: An O / H coating is a thin-film coating that causes water and oil to form beads and become easily removable from a mirror surface, and thus improves cleanability, contamination resistance, and usable life of a mirror.SELECTED DRAWING: Figure 2A

Description

[Technical field]

[0001] (CROSS REFERENCE TO RELATED APPLICATIONS) This application claims priority to U.S. Provisional Patent Application No. 63 / 049,951, filed July 9, 2020, which is hereby incorporated by reference in its entirety.

[0002] (Field) FIELD OF THE DISCLOSURE This disclosure relates generally to coatings for substrates, and more particularly to energetically coupled aluminum and oleo / water repellent (O / H) substrate coatings and methods for forming and using the coatings. [Background technology]

[0003] (background) Coatings including materials such as aluminum, gold, silver, and dielectric materials can be applied to glass articles to make them reflective and create a mirrored surface. Producing optical-quality mirrors, which require a high degree of uniformity and reflectivity, requires greater polishing and precision during the creation and deposition of the coating than, for example, household mirrors, which do not require the same high degree of uniformity and reflectivity. Such optical-quality mirrors are used to reflect light in a wide variety of applications (including but not limited to optical components in light beam steering, interferometers, lighting, and imaging systems) and industries (including but not limited to life sciences, astronomy, meteorology, semiconductors, and photovoltaics).

[0004] An oleo / water repellent (O / H) coating is a thin film coating that is applied to a surface and causes oil and water to bead up and easily fall off or be removed from the surface, rather than spreading over the surface in a thin, even layer. O / H coated glasses are commonly used in eyeglasses, cell phone screens, ATM displays, and other small display devices, especially those with a high contact area. O / H coatings on these items allow the display device to resist the build-up of environmental contaminants and improve the ease of cleaning the device.

[0005] One persistent problem in the manufacture of optical quality mirrors has been the inability to formulate durable coatings that offer improved resistance to abrasion and physical degradation, cleanability, and resistance to blurring. Previous attempts to provide such coatings have generally been characterized by poor adhesion between the coating layer and the substrate, resulting in a short useful life for the coating before it separates from the substrate and / or degrades while remaining on the substrate. In many applications of optical mirrors, the mirror surface may be frequently exposed to scratches or other impacts, and / or debris and environmental contaminants, any of which may damage or destroy the uniformity and reflectivity of the mirror surface. It is therefore very important that mirrors used in these applications are scratch and break resistant and easy to clean, especially since mirrors that are difficult to clean are more susceptible to scratching and breakage (i.e., require more pressure or rubbing force to clean). Thus, a coating for an optical mirror that reduces the adhesion of dirt and contaminants to its surface could provide a dual advantage in improving the cleanability of the mirror as well as the mirror's resistance to wear and physical degradation.

[0006] Thus, there is a need in the art for coatings for optical mirrors that improve both the mirror's resistance to abrasion and other physical damage, and its resistance to contamination and / or ease of cleaning, while maintaining the optical qualities (i.e., uniformity and reflectivity) of the mirror. Additionally, it would be advantageous for such coatings to have improved coating-to-substrate adhesion over prior art coatings. A further need exists for apparatus and methods for creating such coatings and applying them to substrates, most commonly glass substrates. Summary of the Invention [Means for solving the problem]

[0007] (summary) In one embodiment of the present disclosure, an optical mirror includes: (1) a base layer; (2) a binder layer comprising aluminum metal overlaid on and energetically bonded to the base layer; (3) a reflective layer comprising aluminum metal overlaid on the binder layer; (4) a protective layer comprising silicon dioxide overlaid on the reflective layer; and (5) a top layer overlaid on the protective layer, wherein the top layer is at least one of oil-repellent and water-repellent.

[0008] In certain embodiments, the binder layer may be deposited at a first predetermined rate, and the reflective layer may be deposited at a second predetermined rate.

[0009] In certain embodiments, at least one of the binder layer and the protective layer may be deposited by ion-aided deposition, which may be, but need not be, argon ion-assisted deposition.

[0010] In certain embodiments, at least one of the following may be satisfied: (i) the binder layer has a thickness of about 50 angstroms to about 450 angstroms; (ii) the reflective layer has a thickness of about 500 angstroms to about 900 angstroms; (iii) the protective layer has a thickness of about 950 angstroms to about 2350 angstroms; and (iv) the top layer has a thickness of about 100 angstroms to about 300 angstroms.

[0011] In certain embodiments, the optical mirror includes one or more of the preceding embodiments, wherein the combined thickness of the binder layer, the reflective layer, the protective layer, and the top layer may vary by about 2% or less, about 1.5% or less, or about 1% or less across the surface area of ​​the top layer.

[0012] The optical mirror may include one or more of the preceding embodiments, and the first predetermined velocity is optionally less than or equal to about 5 Angstroms / second.

[0013] In some desired embodiments, the first predetermined rate at which the binder layer is deposited is between about 0.1 Angstroms / second and about 5.0 Angstroms / second.

[0014] The optical mirror optionally includes any one or more of the preceding embodiments, wherein the second predetermined velocity is at least about 15 Angstroms / second.

[0015] In some embodiments, the second predetermined rate at which the reflective layer is deposited optionally is between about 15 Angstroms / second and about 50 Angstroms / second.

[0016] In some embodiments, the reflective layer is deposited by a vacuum evaporation aluminum silver plating process.

[0017] The optical mirror may include any one or more of the preceding embodiments, and optionally, a protective layer is deposited on the reflective layer by ion-assisted deposition, optionally argon-ion assisted deposition.

[0018] In some embodiments, the protective layer is deposited onto the reflective layer at a rate of about 2 Angstroms / second to about 5 Angstroms / second.

[0019] The optical mirror can also include one or more of the previous embodiments, and optionally, the protective layer is a first protective layer, and the optical mirror further includes a second protective layer located on top of the first protective layer. Thus, the first protective layer can be optionally a lower protective layer, and the second protective layer can be optionally an upper protective layer.

[0020] In some embodiments, the first protective layer is applied to the reflective layer by ion-assisted deposition.

[0021] The first protective layer optionally has a first thickness of about 950 angstroms to about 1750 angstroms.

[0022] A second protective layer is optionally applied over the first protective layer by a non-ionized vacuum deposition process.

[0023] The second protective layer optionally has a second thickness of from about 1 Angstrom to about 600 Angstroms.

[0024] In some embodiments, the top layer is deposited by ion-assisted deposition. Optionally, the top layer is deposited using an argon ion assisted technique.

[0025] The optical mirror may also include one or more of the previous embodiments, with the top layer optionally including one of Substance WR4-SF Patinal®, Surfclear 100A, and Surfclear 300.

[0026] The optical mirror optionally includes one or more of the preceding embodiments, wherein the substrate comprises glass.

[0027] Alternatively, in some embodiments, the base layer comprises a plastic, metal, or polymer.

[0028] In some embodiments, the average reflectivity of the optical mirror is at least about 85% over the wavelength range of 450 nanometers to 650 nanometers.

[0029] In certain embodiments, the water contact angle on the surface of the top layer is at least about 90°. Additionally or alternatively, the oil contact angle on the surface of the top layer is at least about 70°.

[0030] The optical mirror may also include one or more of the previous embodiments, optionally with the protective layer being washed (or cleaned) before a top layer is applied over the protective layer.

[0031] In some embodiments, the protective layer is cleaned by an ion cleaning method.

[0032] Optionally, the ion source for the ion cleaning process is the same as that used to deposit one or more layers of the optical mirror by ion-assisted deposition.

[0033] In some embodiments, the ion source for the ion cleaning process is argon.

[0034] The optical mirror optionally includes one or more of the preceding embodiments and further includes a front surface that is concave.

[0035] In certain embodiments, the front surface has a radius of curvature of about 9 feet to about 12 feet.

[0036] In some embodiments, the optical mirror includes one or more of the previous embodiments, with the front surface shaped to collimate light scattered from a diffusing screen illuminated by the projector.

[0037] The optical mirror may also include one or more of the previous embodiments, where the front surface has a shape that includes at least a portion of a spherical, parabolic, elliptical, and combinations thereof.

[0038] In some embodiments, the optical mirror includes a body having a first side opposite a second side. Optionally, the first side is opposite to (or congruent with) the second side. Additionally or alternatively, the first and second sides may be oriented approximately perpendicular to a front surface of the mirror.

[0039] In certain embodiments, the optical mirror includes one or more of the preceding embodiments, wherein the base layer is part of the body. Alternatively, in another embodiment, the base layer is formed of a first material and the body includes a second material different from the first material. The base layer is bonded or interconnected with the body.

[0040] In some embodiments, the base layer is bonded or interconnected to the body before the binder layer is bonded to the base layer.

[0041] Alternatively, one or more of the binder layer, reflective layer, protective layer, and top layer may be applied to the base layer before the base layer is bonded or interconnected to the body.

[0042] In another embodiment of the present disclosure, a coating for an optical mirror comprises: (1) a binder layer comprising aluminum metal deposited on an underlying substrate at a first rate; (2) a reflective layer comprising aluminum metal deposited at a second rate and overlying the binder layer; (3) a protective layer comprising silicon dioxide overlying the reflective layer; and (4) a top layer overlying the protective layer, wherein the top layer is at least one of oil- and water-repellent.

[0043] In certain embodiments, at least one of the binder layer and the protective layer may be deposited by ion-assisted deposition, which may, but need not, be argon-ion assisted deposition.

[0044] In certain embodiments, at least one of the following may be satisfied: (i) the binder layer has a thickness of about 50 angstroms to about 450 angstroms; (ii) the reflective layer has a thickness of about 500 angstroms to about 900 angstroms; (iii) the protective layer has a thickness of about 950 angstroms to about 2350 angstroms; and (iv) the top layer has a thickness of about 100 angstroms to about 300 angstroms.

[0045] In certain embodiments, the combined thickness of the binder layer, reflective layer, protective layer, and top layer may vary by no more than about 2%, no more than about 1.5%, or no more than about 1% across the surface area of ​​the coating.

[0046] The coating may also include one or more of the preceding embodiments, wherein the first rate at which the binder layer is deposited is less than or equal to about 5 Angstroms / second.

[0047] In some embodiments, the first rate at which the binder layer is deposited on the base layer is from about 0.1 Angstroms / second to about 5.0 Angstroms / second.

[0048] In certain embodiments, the coating optionally comprises any one or more of the preceding embodiments, and the second rate can be at least about 15 Angstroms / second.

[0049] In some embodiments, the reflective layer may be deposited at a second rate of from about 15 Angstroms / second to about 50 Angstroms / second.

[0050] In some embodiments, the reflective layer is deposited by a vacuum evaporation aluminum silvering process.

[0051] The coating may also include any one or more of the preceding embodiments, and optionally, the protective layer is deposited on the reflective layer by ion-assisted deposition, optionally argon-ion assisted deposition.

[0052] The coating can include one or more of the preceding embodiments, and optionally, the protective layer is a first protective layer, and the coating further includes a second protective layer located between the first protective layer and the top layer. Thus, the first protective layer can optionally be a lower protective layer, and the second protective layer can optionally be an upper protective layer.

[0053] In another embodiment of the present disclosure, a method of making an optical mirror includes: (a) applying a binder layer comprising aluminum metal to a substrate at a first rate; (b) applying a reflective layer comprising aluminum metal on the binder layer at a second rate; (c) applying a protective layer comprising silicon dioxide on the reflective layer to form an uncoated optical mirror; and (d) applying a top layer on the protective layer to form a coated optical mirror, wherein the top layer is at least one of oil- and water-repellent.

[0054] In certain embodiments, at least one of the binder layer and the protective layer may be deposited by ion-assisted deposition, which may be, but need not be, argon-ion assisted deposition.

[0055] In certain embodiments, at least one of the following may be satisfied: (i) the binder layer has a thickness of about 50 angstroms to about 450 angstroms; (ii) the reflective layer has a thickness of about 500 angstroms to about 900 angstroms; (iii) the protective layer has a thickness of about 950 angstroms to about 2350 angstroms; and (iv) the top layer has a thickness of about 100 angstroms to about 300 angstroms.

[0056] In certain embodiments, the combined thickness of the binder layer, reflective layer, protective layer and top layer may vary by no more than about 2%, no more than about 1.5%, or no more than about 1% across the surface area of ​​the substrate.

[0057] In certain embodiments, the oil / water repellent material of the top layer may be selected from the group consisting of Substance WR4-SF Patinal®, Surfclear 100, and Surfclear 300.

[0058] In certain embodiments, the average reflectance of the optical mirror over the wavelength range of 450 nanometers to 650 nanometers can be at least about 85%.

[0059] In embodiments, the optical mirror optionally includes one or more of the preceding embodiments, and further includes a front surface that is concave.

[0060] In certain embodiments, the radius of curvature of the front surface of the optical mirror may be at least about 9.25 feet.

[0061] In certain embodiments, the front surface has a radius of curvature of about 9 feet to about 12 feet.

[0062] In certain embodiments, the water contact angle with respect to the front surface of the optical mirror may be at least about 90°.

[0063] In certain embodiments, the oil contact angle on the front surface of the optical mirror may be at least about 70°.

[0064] In certain embodiments, the vacuum chamber in which steps (c) and (d) are performed may not be purged or vented between steps (c) and (d).

[0065] The method may include one or more of the preceding embodiments and may further include ionically cleaning the uncoated optical mirror between steps (c) and (d). The duration of the ionically cleaning step may optionally, but not necessarily, be between about 1 minute and about 30 minutes. The ionically cleaning step may optionally, but not necessarily, be an argon ion cleaning step.

[0066] The method can also include one or more of the preceding embodiments, and optionally, the protective layer is a first protective layer, and the method further includes applying a second protective layer located between the first protective layer and the top layer. Thus, the first protective layer can optionally be a bottom protective layer, and thus the second protective layer can optionally be a top protective layer.

[0067] In some embodiments, the first protective layer is applied to the reflective layer by ion-assisted deposition.

[0068] The first protective layer optionally has a first thickness of about 950 angstroms to about 1750 angstroms.

[0069] A second protective layer is optionally applied over the first protective layer by a non-ionized vacuum deposition process.

[0070] The second protective layer optionally has a second thickness of from about 1 Angstrom to about 600 Angstroms.

[0071] The method may include one or more of the preceding embodiments and may further include depositing the binder layer at a first rate of about 5 Angstroms / second or less.

[0072] In some embodiments, the first rate at which the binder layer is deposited on the substrate is from about 0.1 Angstroms / second to about 5.0 Angstroms / second.

[0073] In certain embodiments, the method optionally includes any one or more of the preceding embodiments, wherein the second rate can be at least about 15 Angstroms / second.

[0074] In some embodiments, the second rate at which the reflective layer is deposited is between about 15 Angstroms / second and about 50 Angstroms / second.

[0075] In some embodiments, the reflective layer is deposited by a vacuum evaporation aluminum silver plating process.

[0076] In certain embodiments, the time interval between steps (c) and (d) may be about 60 minutes or less.

[0077] The method may include any one or more of the preceding embodiments, and optionally, the protective layer is deposited on the reflective layer by ion-assisted deposition. The ion-assisted deposition is optionally argon-ion assisted deposition.

[0078] In certain embodiments, the method includes any one or more of the preceding embodiments, further comprising depositing the top layer by ion-assisted deposition.

[0079] Optionally, the top layer is deposited using an argon ion-assisted technique.

[0080] In some embodiments, the method further comprises providing a substrate formed of glass.

[0081] Alternatively, in some embodiments, the method further comprises providing a substrate formed of a plastic, metal, or polymer.

[0082] The method optionally includes one or more of the preceding embodiments, further including bonding the substrate to the body of the optical mirror.

[0083] In some embodiments, the substrate is bonded or interconnected to the body before the binder layer is applied to the substrate.

[0084] Alternatively, one or more of the binder layer, reflective layer, protective layer and top layer may be applied to the substrate prior to bonding or interconnecting the substrate to the body.

[0085] One aspect of the present disclosure is a mirror substantially as described herein. The mirror may include any of the aspects and embodiments described herein. The mirror may be formed by any method or combination of methods described herein.

[0086] Another aspect of the present disclosure is a coating for an optical mirror substantially as described herein. The coating may include any of the aspects and embodiments described herein. The coating may be applied to the optical mirror by any method or combination of methods described herein.

[0087] One embodiment is a mirror having a coating substantially as described herein.

[0088] Yet another aspect of the present disclosure is a method of manufacturing a coated optical mirror substantially as described herein. The method may include any of the aspects and embodiments described herein.

[0089] Yet another aspect is a mirror substantially manufactured by the methods described herein.

[0090] Advantages of the present invention will be apparent from the disclosure contained herein.

[0091] As used herein, "at least one," "one or more," and "and / or" are open-ended expressions that are both conjunctive and disjunctive in operation. For example, "at least one of A, B, and C," "at least one of A, B, or C," "one or more of A, B, and C," and "one or more of A, B, or C" mean A alone, B alone, C alone, A and B together, A and C together, B and C together, or A, B, and C together.

[0092] It should be noted that the term "a" or "an" refers to one or more of that entity. Thus, the terms "a" (or "an"), "one or more," and "at least one" can be used interchangeably herein. It should also be noted that the terms "comprising," "including," and "having" can be used interchangeably.

[0093] Unless otherwise specified, all numerical values ​​expressing quantities, dimensions, conditions, ratios, ranges, etc. used in the specification and claims should be understood to be modified in all cases by the term "about" or "approximately". Thus, unless otherwise specified, numerical values ​​expressing quantities, dimensions, conditions, ratios, ranges, etc. used in the specification and claims may be increased or decreased by about 5% to obtain adequate (or satisfactory) results. In addition, if the meaning of the term "about" or "approximately" as used herein is not otherwise clear to a person skilled in the art, the term "about" or "approximately" should be interpreted to mean within plus or minus 10% of the stated value.

[0094] All ranges described herein may be expanded to any subrange or portion of that range, or to any value within that range, without departing from the invention. For example, the range "5 to 55" includes, but is not limited to, the subranges "5 to 20" and "17 to 54."

[0095] Unless otherwise specified, the term "substantially" indicates that a variance of 0% to 5% of the stated value is permitted.

[0096] The embodiments and configurations described herein are neither complete nor exhaustive, and it will be understood that other embodiments of the invention can utilize, alone or in combination, one or more of the features described above or detailed below. [Brief description of the drawings]

[0097] [Figure 1] FIG. 1 is a perspective view of a mirror according to an embodiment of the present disclosure. [Figure 2A] FIG. 2A is an illustration showing layers of a mirror having an energetically coupled O / H coating according to an embodiment of the present disclosure. [Figure 2B] FIG. 2B is an illustration showing layers of another mirror having an energetically coupled O / H coating according to an embodiment of the present disclosure. [Diagram 3] FIG. 3 is an illustration of a method for manufacturing a mirror having an energetically coupled O / H coating according to an embodiment of the present disclosure. [Figure 4] FIG. 4 is an illustration of another method for fabricating a mirror having an energetically coupled O / H coating according to an embodiment of the present disclosure. [Figure 5A-5B] 5A and 5B are photographs of a conventional mirror and a mirror having an energetically coupled O / H coating according to an embodiment of the present disclosure, respectively, after a "tape pull" adhesion test. [Figure 6A-6B]6A and 6B are perspective views of a conventional mirror and a mirror having an energetically coupled O / H coating according to an embodiment of the present disclosure, respectively, with water droplets applied to their surfaces. [Figure 7A-7B] 7A and 7B are close-up views of water droplets applied to the surface of the conventional mirror of FIG. 6A and the mirror with energetically coupled O / H film of FIG. 6B, respectively. [Figure 8A-8B] 8A and 8B are photographs, respectively, of a conventional mirror and a mirror having an energetically coupled O / H coating according to an embodiment of the present disclosure with a fingerprint applied to its surface. [Figure 9A-9B] 9A and 9B are photographs of the mirrors of FIGS. 8A and 8B, respectively, after they have been rubbed with a dry paper towel. [Figure 10A-10B] 10A and 10B are photographs of a conventional mirror and a mirror having an energetically coupled O / H coating according to an embodiment of the present disclosure, respectively, with permanent ink applied to its surface. [Figure 11A-11B] 11A and 11B are photographs of the mirrors of FIGS. 10A and 10B, respectively, after they have been rubbed with a dry paper towel. [Figure 12A-12B] 12A and 12B are photographs of a mirror having an energetically coupled O / H coating according to an embodiment of the present disclosure after application of a foaming spray cleaner and after wiping the foaming spray cleaner off with a dry microfiber cloth, respectively. [Figure 13A-13B] 13A and 13B are photographs of two conventional mirrors and two mirrors having energetically coupled O / H coatings according to embodiments of the present disclosure, respectively, after a salt spray test. [Figure 14] FIG. 14 is a graph of the reflectivity of a conventional mirror and a mirror having an energetically coupled O / H coating according to an embodiment of the present disclosure. [Figure 15A-15B]15A and 15B are photographs of a conventional mirror and a mirror having an energetically coupled O / H coating according to an embodiment of the present disclosure, respectively, after a "tape pull" adhesion test. [Figure 16A-16B] 16A and 16B are photographs of a conventional mirror and a mirror having an energetically coupled O / H coating according to an embodiment of the present disclosure, respectively, with water droplets applied to their surfaces. [Figure 17A-17B] 17A and 17B are close-up views of the mirrors of FIGS. 16A and 16B with water droplets on their surfaces, respectively. [Figure 18A-18B] 18A and 18B are photographs, respectively, of a conventional mirror and a mirror having an energetically coupled O / H coating according to an embodiment of the present disclosure with a fingerprint applied to its surface. [Figure 19A-19B] 19A and 19B are photographs of the mirrors of FIGS. 18A and 18B, respectively, after they have been rubbed with a dry paper towel. [Figure 20A-20B] 20A and 20B are photographs of a conventional mirror and a mirror having an energetically coupled O / H coating according to an embodiment of the present disclosure, respectively, on whose surface permanent ink has been applied. [Figure 21A-21B] 21A and 21B are photographs of the mirrors of FIGS. 20A and 20B, respectively, after they have been rubbed with a dry paper towel. [Figure 22] FIG. 22 is a photograph of seven sample mirrors, each having an energetically coupled O / H coating according to an embodiment of the present disclosure. [Figure 23] FIG. 23 is a graph of the reflectivity of a conventional mirror and a mirror having an energetically coupled O / H coating according to an embodiment of the present disclosure. [Figure 24A] FIG. 24A is a graph of the reflectivity of the sample mirror with the energetically coupled O / H coating of FIG. [Figure 24B] FIG. 24B is a graph of the reflectivity of the sample mirror with the energetically coupled O / H coating of FIG. [Figure 24C] FIG. 24C is a graph of the reflectivity of the sample mirror with the energetically coupled O / H coating of FIG. [Figure 24D] FIG. 24D is a graph of the reflectivity of the sample mirror with the energetically coupled O / H coating of FIG. [Figure 24E] FIG. 24E is a graph of the reflectivity of the sample mirror with the energetically coupled O / H coating of FIG. [Figure 24F] FIG. 24F is a graph of the reflectivity of the sample mirror with the energetically coupled O / H coating of FIG. [Figure 24G] FIG. 24G is a graph of the reflectivity of the sample mirror with the energetically coupled O / H coating of FIG. [Diagram 25] FIG. 25 is a graph showing the variation in thickness of the mirror coating of FIG. [Figure 26] FIG. 26 is a photograph of a portion of a full size conventional mirror with an O / H coating according to an embodiment of the present disclosure applied to its surface with permanent ink. [Figure 27] FIG. 27 is a photograph of another portion of the full-size conventional mirror of FIG. 26 with water droplets applied to its surface. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Detailed Description of the Invention

[0098] (Detailed Description) Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. All patents, applications, published applications and other publications referenced herein are incorporated herein in their entirety by reference. In the event that there are multiple definitions for terms herein, the definitions provided in the summary shall prevail unless otherwise specified.

[0099] The term "hydrophobic" as used herein, unless otherwise specified, refers to a material that appears or tends to repel water, or that appears or tends to be repelled by water, or to which water tends to adhere poorly.

[0100] The term "oleophobic" as used herein, unless otherwise specified, refers to a material which appears or tends to repel oil and oily substances, or which appears or tends to be repelled by oil and oily substances, or to which oil and oily substances tend to adhere poorly.

[0101] As used herein, the terms "oil / water repellent" and "O / H" are interchangeable unless otherwise specified and each refers to a material that is either oil repellent or water repellent, or both.

[0102] As used herein, unless otherwise specified, the term "specular reflection" means that light is reflected from a surface at the same angle to the surface normal as the incident light ray, but on the opposite side of the surface normal in the plane formed by the incident and reflected light rays. Reflection that is not specular is "diffuse reflectivity."

[0103] For purposes of further disclosure and to satisfy applicable description and enablement requirements, the following references relate generally to oleophobic and / or hydrophobic coatings, protective coatings for optical quality mirrors, and related compositions, apparatus, methods and systems, and are hereby incorporated by reference in their entirety:

[0104] Military Standard MIL-M-13508C, Mirror, Front Surface Aluminized: For Optical Elements, United States Army Research, Development, and Engineering Command, 19 March 1973.

[0105] Military Standard MIL-C-675C, Coating of Glass Optical Elements (Anti-Reflection), United States Army Research, Development, and Engineering Command, 22 August 1980.

[0106] U.S. Patent No. 7,055,954, issued to Marechal on June 6, 2006, and entitled "Scratch masking coatings for optical substrates" ("Marechal").

[0107] U.S. Patent No. 7,629,053, issued to Lacan et al. on December 8, 2009, entitled “Process for treating an ophthalmic lens” ("Lacan").

[0108] U.S. Patent No. 9,896,549, issued February 20, 2018 to Kessman et al., entitled “Hydrophobic and oleophobic coatings” (“Kessman”).

[0109] The present disclosure provides protective coatings for surfaces of substrates, particularly glass substrates, and more particularly optical mirrors, that include multiple layers. The coating layers include energetically coupled layers of aluminum and oleophobic (O / H) materials to provide the mirror with improved resistance to abrasion and physical degradation, cleanability, resistance to fogging, and adhesion of the coating to the substrate. The present disclosure also provides methods of forming and using such protective coatings.

[0110] The application of coatings of the present disclosure to optical quality mirrors increases the cleanability and useful life of the mirror, reduces the likelihood of the mirror being damaged by environmental contaminants, and reduces the mirror's susceptibility to reflective and transmissive haze. The method of depositing the coatings on a substrate can be easily incorporated into or created from existing methods for manufacturing such mirrors, providing a mirror having these and other advantages and benefits with minimal added time (in some embodiments, about 10 minutes) and cost (in some embodiments, about $200).

[0111] Water that accumulates on the surface of an optical quality mirror can, over time, penetrate the top layer of the mirror's coating, causing chemical or physical degradation of the layer. In addition, prolonged contact of the top surface of the coating with water can cause contaminants dissolved in the water to leach and be absorbed into the coating, resulting in a "blue haze" or "white haze" phenomenon that not only reduces the reflectivity of the mirror, but can also be very difficult to clean or remove from the mirror without abrading or damaging parts of the coating itself. Thus, in embodiments, the present disclosure can provide important advantages and benefits of improving the water repellency of the mirror coating, reducing the amount of water that can accumulate on the surface and the length of time such water can remain before it falls off or is otherwise removed from the surface.

[0112] 1, one embodiment of a mirror 10 of the present disclosure is generally shown. Mirror 10 generally includes a body 12 having a front surface 14 opposed to a rear surface 16, a top surface 18 opposed to a bottom surface 20, and a first side 22 opposed to a second side 24. Body 12 can have any shape and geometry. In embodiments, body 12 is formed from one or more of glass, metal, polymer, and plastic.

[0113] The front surface 14 may have any predetermined shape. In embodiments, the front surface 14 is curved. For example, the front surface 14 may be generally concave. The front surface 14 may have a spherical, elliptical, freeform, planar, and other shapes known to those skilled in the art. In embodiments, the front surface 14 of the mirror body 12 has a shape that includes at least a portion of a circle, a sphere, a parabolic, an elliptical, a planar, a freeform, and combinations thereof. In some embodiments, the front surface 14 has a geometry adapted to collimate light from a projector to a user facing the front surface.

[0114] The front portion 14 may have a predetermined radius of curvature. In embodiments, the front portion 14 has a radius of curvature between about 9 feet and about 12 feet. Optionally, the radius of curvature is about 9.25 feet, about 10 feet, or about 11 feet. In other embodiments, the radius of curvature may be less than 9 feet or greater than 12 feet.

[0115] As generally shown in FIG. 1, in an embodiment, the first and second sides 22, 24 of the mirror body 12 are generally vertically oriented. In an embodiment, the first side 22 is a mirror image of (or faces) the second side 24. In addition, the sides 22, 24 are optionally planar. The sides 22, 24 may also be described as having a radial shape that coincides with the center of curvature of the front surface 14 such that, when arranged in a mirror array including multiple mirror bodies, the sides of the mirror body 12 coincide with the sides of adjacent mirror bodies. The radial sides 22, 24 may be approximately perpendicular, or "plumb," to the front surface 14.

[0116] 2A, one embodiment of a coating 100A on the front surface 14 of a mirror 10A is generally shown. The coating 100A includes an energetically coupled O / H top layer 160. More specifically, the front surface 14 includes a base layer (or substrate layer) 110, a binder layer 120, a reflective layer 130, a protective layer 140, and a top layer (or O / H layer) 160.

[0117] The base layer 110 is a substrate to which the coating 100A of the present disclosure (i.e., the coating including the binder layer 120, the reflective layer 130, the protective layer 140, and the top layer 160) may be applied. The base layer 110 may be part of the mirror body 12. Alternatively, the base layer 110 may be a material bonded or attached to the mirror body 12. For example, in some embodiments, the base layer 110 is formed of a first material and the mirror body 12 is formed of a second, different material.

[0118] The substrate 110 is most commonly made entirely or primarily of glass, but in embodiments may be made entirely or primarily of any of a number of other suitable materials, including, but not limited to, metals, metal alloys, and / or plastics. The properties of the substrate 110 may be selected or controlled to provide a mirror of desired quality or to have desired properties; in particular, the surface quality (i.e., deviations from an ideal shape) of the substrate 110 affects properties such as distortion, artifacts, aberrations, coherence, collimation, and divergence, and the surface roughness of the substrate 110 determines how specular and how diffuse the reflection will be, and thus can control the sharpness (or blurriness) of the image.

[0119] As described further herein, the coatings of the present disclosure, and methods of making and applying such coatings, are particularly advantageous in that they do not significantly alter, scratch, or goug the surface quality of the substrate 110, thereby minimizing surface roughness introduced by the coating process. It is expressly understood that the substrate 110 (and thus the mirror 10A as a whole) can be of any suitable material, length, width, or area. As a non-limiting example, a mirror 10 for use in, for example, a flight vehicle simulator (FVS) can have a radius of curvature that is about 9.25 feet, about 10 feet, or about 11 feet.

[0120] The binder layer 120 is on the base layer 110 and is the first layer of the coating 100A to be deposited on the base layer 110. The primary purpose of the binder layer 120 is to improve adhesion between the subsequently deposited layers of the coating (i.e., the reflective layer 130, the protective layer 140, and the top layer 160) and the base layer 110. This effect is achieved by providing the binder layer 120, particularly in the form of aluminum metal, in a thin layer - for example, about 50 angstroms to about 450 angstroms, most commonly about 250 angstroms - by energetically bonding the aluminum binder layer 120 to the base layer 110. This energetic bonding can be achieved by depositing the binder layer 120 on the base layer 110 by vacuum deposition, and in some embodiments, ion-assisted deposition (IAD). IAD is a type of vacuum deposition process in which a substrate is bombarded, either continuously or periodically, with energetic particles during deposition, resulting in the deposition of atomic-sized energetic particles of the deposited condensed film material. The energetic particles bombarding the substrate are usually ions of an inert gas, but can be ions of a reactive gas or of the condensed film material itself. In some embodiments, the ions can be argon ions, and thus the process can be referred to as "argon IAD."

[0121] While one of ordinary skill in the art would be able to select appropriate operating parameters for the IAD process to deposit the binder layer 120, the inventors have discovered that one important consideration for this step is a relatively slow rate of deposition. By way of non-limiting example, the binder layer 120 may be deposited on the base layer 110 at a rate of about 5.0 Angstroms / second or less, about 4.5 Angstroms / second or less, about 4.0 Angstroms / second or less, about 3.5 Angstroms / second or less, about 3.0 Angstroms / second or less, about 2.5 Angstroms / second or less, about 2.0 Angstroms / second or less, about 1.5 Angstroms / second or less, about 1.0 Angstroms / second or less, or about 0.5 Angstroms / second. In some embodiments, the binder layer 120 is deposited on the base layer 110 at a rate of about 0.1 Angstroms / second to about 5.0 Angstroms / second. Without wishing to be bound by any particular theory, it is hypothesized that these relatively low deposition rates provide the greatest degree of energetic bonding between the binder layer 120 and the substrate 110, and thus provide the greatest improvement in adhesion between subsequently deposited layers of the coating and the substrate 110.

[0122] The reflective layer 130 is on the binder layer 120 and is deposited after the binder layer 120 is deposited. The reflective layer 130 - like the binder layer 120, comprises aluminum metal - is the light reflective portion of the mirror 10A, i.e., enhances the reflectivity of the substrate 110 and thus the mirror 10A as a whole. Aluminum, well known as the "silvering" material in many devices, particularly telescopes, conventional optical quality mirrors, is harder and less expensive than silver, reflects 85%-90% of incident visible light, and tarnishes relatively quickly, but does not interfere with the reflectivity of the coating because the tarnish (i.e., aluminum oxide) is itself transparent. The reflective layer 130 is generally thicker than the binder layer 120, typically about 500 Angstroms to about 900 Angstroms, most commonly about 700 Angstroms.

[0123] The reflective layer 130 may be deposited by conventional vacuum evaporated aluminum silver plating processes, as are well known and widely practiced in the art, however, the inventors have discovered that, unlike the binder layer 120, the reflective layer 130 generally benefits from a relatively high deposition rate.

[0124] As non-limiting examples, the reflective layer 130 may be deposited at a rate of at least about 15 Angstroms / sec, at least about 20 Angstroms / sec, at least about 25 Angstroms / sec, at least about 30 Angstroms / sec, at least about 35 Angstroms / sec, at least about 40 Angstroms / sec, at least about 45 Angstroms / sec, or about 50 Angstroms / sec. In some embodiments, the reflective layer 130 is deposited at a rate of about 15 Angstroms / sec to about 50 Angstroms / sec. Without wishing to be bound by any particular theory, it is hypothesized that these relatively high deposition rates allow the reflective layer 130 to be energetically coupled to the binder layer 120 without disrupting the energetic coupling between the binder layer 120 and the base layer 110, thereby maintaining the improved adhesion effect of the binder layer 120.

[0125] The protective layer 140 is on the reflective layer 130 and is deposited after the deposition of the reflective layer 130. The material of the protective layer 140, typically silicon dioxide, can serve a dual purpose: it is generally a hard material that protects the reflective layer 130 from damage and improves the durability, wear resistance, etc. of the mirror 10A as a whole, but can also be a dielectric material, thus greatly enhancing the reflectivity of the mirror 10A at a desired wavelength or wavelengths. The thickness of the protective layer 140 can be selected to provide a desired dielectric effect, but generally the protective layer 140 can be significantly thicker than the binder layer 120 and / or the reflective layer 130. In embodiments, the thickness of the protective layer 140 can be from about 950 angstroms to about 2350 angstroms, most typically about 1650 angstroms.

[0126] The protective layer 140, like the binder layer 120, is most advantageously deposited by IAD. The deposition rate of the protective layer 140 is not critical, and any suitable rate as known and described in the art may be selected for the desired application. In some embodiments, due to similar considerations as discussed above with respect to the binder layer 120, a relatively low deposition rate may be desirable, for example, from about 2 Angstroms / sec to about 5 Angstroms / sec, or about 2.5 Angstroms / sec.

[0127] Top layer 160 is on top of protective layer 140 and is deposited after deposition of protective layer 140. Top layer 160 defines an exterior surface 170 of front portion 14 of mirror 10A.

[0128] The top layer 160 is made from an oleo / water repellent (O / H) material and functions to improve the cleanability and stain / soil resistance of the mirror 10A. In particular, the O / H top layer 160 causes oil-based (oils present on human skin) or water-based (e.g., environmental water vapor, rainfall, human body fluids, etc.) contaminants to "bead" on the surface of the mirror 10A, rather than spreading across the surface in a thin layer; thus, the contact area between the contaminant and the surface is minimized, facilitating the contaminant to fall off and / or be removed from the surface. The O / H top layer 160 thus extends the useful life of the mirror 10A by reducing both the frequency and force required to keep the mirror 10A clean, thereby reducing the possibility of damage to the mirror 10A as a result of cleaning.

[0129] While the deposition rate of top layer 160 is not critical and any suitable rate as known and described in the art may be selected depending on the desired application, the inventors have discovered that it is generally advantageous to apply top layer 160 immediately or shortly (e.g., within about 60 minutes) after deposition of protective layer 140. Without wishing to be bound by any particular theory, it is believed that application of top layer 160 over the recently deposited protective layer 140 may result in a more effective bond between protective layer 140 and top layer 160 and / or a more uniform thickness of top layer 160.

[0130] Top layer 160 may be made of any O / H material suitable for making O / H coatings on glass surfaces such as touch screens, so long as such material can be evaporated (thermally or by electron beam) in a vacuum deposition chamber without depositing unwanted by-products or contaminants on mirror 10A. Examples of O / H materials suitable for use in top layer 160 include, but are not limited to, Substance WR4-SF Patinal® (EMD Performance Materials, Darmstadt, Germany), Surfclear 100 (Canon Optron, Inc., Yuki, Japan), and Surfclear 300 (Canon Optron, Inc., Yuki, Japan). Top layer 160 may typically have a thickness of about 100 Angstroms to about 300 Angstroms, most typically about 150 Angstroms.

[0131] In some embodiments, the efficiency and effectiveness of the top layer 160 and / or its deposition process may be improved by performing an ion cleaning of the mirror 10A after application of the protective layer 140 and before application of the top layer 160. Ion cleaning, like IAD, is a process of bombarding the substrate surface with energetic atomic-sized particles, but differs in that it occurs in the presence of condensed film material. As a result, the ion bombardment produces atoms or molecules, often contaminating atoms or molecules, that must be removed from the substrate surface. The inventors have found that the incorporation of an ion cleaning step between the deposition of the protective layer 140 and the deposition of the top layer 160 can beneficially remove contaminants and improve the uniformity of the mirror surface (i.e., to "smooth" or reduce roughness of the mirror surface that may be introduced as a result of non-uniform deposition of either the protective layer 140 and / or the underlying layers 110, 120, 130) prior to application of the O / H coating 160. In this manner, the incorporation of an ion cleaning step can provide a mirror 10 with the surface uniformity and optical qualities characteristic of high performance mirrors, while also including the full advantages of the O / H coatings discussed throughout this disclosure. Additionally, if the ion source is the same as that used for deposition of any one or more of the mirror's IAD deposition layers (e.g., using argon ions for ion cleaning where the IAD deposition layers are deposited with argon IAD), the ion cleaning can be performed during the same manufacturing run as the other layer deposition steps and / or without venting the vacuum chamber, further improving the efficiency and cost-effectiveness of the manufacturing method.

[0132] One particular advantage and benefit of the mirror 10A and coating 100A illustrated in FIG. 2A is that it can provide an improved O / H effect (provided by the top layer 160) while maintaining a uniform coating thickness across the entire area of ​​the mirror 10A. Prior attempts to provide O / H coatings on optical quality mirrors have typically suffered from very poor coating thickness uniformity. Often, the coating thickness of these prior mirrors varies by at least as much as 6% across the area of ​​the mirror, and such large variations in coating thickness can significantly degrade the optical performance of the mirror. In contrast, the inventors can provide a mirror 10A according to the embodiment shown in FIG. 2A in which the coating thickness varies by about 2% or less, and in some cases about 1.5% or less, or about 1% or less, across the area of ​​the mirror's front surface 14, thereby maintaining the optical quality of the mirror while providing the desired O / H effect.

[0133] 2B, another embodiment of a mirror 10B is illustrated having a coating 100B including an energetically coupled O / H top layer 160. The embodiment illustrated in FIG. 2B is similar to that illustrated in FIG. 2A, except that a portion of the protective layer 140 is replaced with a second (or top) protective layer 150. Typically, in the mirror 10B according to the embodiment illustrated in FIG. 2B, the lower protective layer 140 is applied by IAD, while the upper protective layer 150 is applied by a non-ion assisted vacuum deposition process. Without wishing to be bound by any particular theory, it is possible that the application of a portion of the protective layer(s) without using IAD may provide an advantageous difference in chemical, optical, or physical properties, or a combination thereof, between the lower protective layer 140 and the upper protective layer 150.

[0134] The thickness of the top protective layer 150 can typically be from about 1 Angstrom to about 600 Angstroms, most typically about 300 Angstroms, but the combined thickness of the lower and upper protective layers 140, 150 in the embodiment illustrated in Figure 2B is typically approximately equal to the thickness of the single protective layer 140 in the embodiment illustrated in Figure 2A, e.g., from about 950 Angstroms to about 2350 Angstroms, most typically about 1650 Angstroms. As in the embodiment illustrated in Figure 2A, in the manufacturing process of the mirror 10B illustrated in Figure 2B, after deposition of the second / top protective layer 150 and before deposition of the top layer 160, it may be beneficial to perform an ion cleaning step for any or all of the reasons discussed above.

[0135] Referring now to Figure 3, a method 300 for applying an energetically coupled O / H coating to a mirror 10 is illustrated. Although a general order of operations of method 300 is illustrated in Figure 3, method 300 may include more or fewer operations, or the order of operations may be arranged differently than that illustrated in Figure 3. Additionally, although the operations of method 300 may be described sequentially, one or more operations may actually be performed in parallel or simultaneously.

[0136] In a substrate providing step 310, a substrate or base layer is provided as described above with respect to the base layer 110 illustrated in Figures 1 and 2. In some embodiments, the base layer 110 is the front surface 14 of the mirror body 12. Alternatively, the base layer 110 can include a piece of material such as an insert that is interconnected to the front surface 14.

[0137] In a binder layer deposition step 320, a binder layer is deposited on the base layer 110 as described above with respect to the binder layer 120 illustrated in Figures 2A and 2B. In a reflective layer deposition step 330, a reflective layer is deposited on the binder layer as described above with respect to the reflective layer 130 illustrated in Figures 2A and 2B. In a protective layer(s) deposition step 340, at least one protective layer is deposited on the reflective layer as described above with respect to the protective layer 140 illustrated in Figure 2A and / or with respect to the lower and upper protective layers 140, 150 illustrated in Figure 2B. In a top layer deposition step 360, an O / H top layer is deposited on the protective layer(s) as described above with respect to the top layer 160 illustrated in Figures 2A and 2B.

[0138]

[0036] Referring now to Figure 4, a method 400 for applying an energetically coupled O / H coating to a mirror 10 is illustrated. Although a general order of operations of method 400 is illustrated in Figure 4, method 400 may include more or fewer operations, or the order of operations may be arranged differently than that illustrated in Figure 4. Additionally, although the operations of method 400 may be described sequentially, one or more operations may actually be performed in parallel or simultaneously.

[0139] In a substrate providing step 410, a substrate or base layer is provided as described above with respect to the base layer 110 illustrated in Figures 2A and 2B. In some embodiments, the base layer 110 is the front surface 14 of the mirror body 12. Alternatively, the base layer 110 can include a piece of material such as an insert that is interconnected to the front surface 14.

[0140] In a binder layer deposition step 420, a binder layer is deposited on the base layer, as described above with respect to the binder layer 120 illustrated in Figures 2A and 2B. In a reflective layer deposition step 430, a reflective layer is deposited on the binder layer, as described above with respect to the reflective layer 130 illustrated in Figures 2A and 2B. In a protective layer(s) deposition step 440, at least one protective layer is deposited on the reflective layer, as described above with respect to the protective layer 140 illustrated in Figure 2A and / or with respect to the lower and upper protective layers 140, 150 illustrated in Figure 2B.

[0141] In an argon ion cleaning step 450, the mirror is subjected to an argon ion cleaning process for any length of time suitable to clean, without undesirable etching, the protective layer 140 (or protective layers 140, 150) prior to application of the energetically coupled O / H coating. In embodiments, the argon ion cleaning may last from about 1 minute to about 30 minutes, most typically about 15 minutes. In a top layer deposition step 460, an O / H top layer is deposited over the protective layer(s), as described above with respect to the top layer 160 illustrated in Figures 2A and 2B. EXAMPLES

[0142] The following disclosed examples illustrate and describe various embodiments and features of the present disclosure.

[0143] Example 1: Manufacturing of O / H coated mirror Mirrors for testing the effectiveness of the O / H coatings of the present disclosure were formed by vacuum deposition, specifically by depositing a 700 angstrom layer of aluminum by high rate, non-IAD vacuum deposition on a glass substrate, followed by deposition of a 1650 angstrom layer of silicon dioxide on the aluminum layer by argon IAD. Finally, immediately after the deposition of the final silicon dioxide layer, without venting the deposition chamber, four tungsten boats (Kurt J. Lesker Company, Jefferson Hills, PA) were placed in the resistive source of the S36 coating chamber and two "pills" or "tablets" of the O / H coating material, specifically the material WR4- SF Patinal® (EMD Performance Materials, Darmstadt, Germany), were added to each boat. The O / H material was then deposited by vacuum deposition on the final silicon dioxide to form a finished optical quality mirror with an energetically coupled O / H coating. The coating of the finished mirror consisted of (ascending from the substrate) a binder layer of aluminum metal (low deposition rate (or low deposition rate)) with a thickness of about 250 Angstroms. The substrate included a reflective layer of aluminum metal having a thickness of about 700 Angstroms (applied at a high deposition rate), an IAD deposited protective layer of silicon dioxide having a thickness of about 1350 Angstroms, a non-IAD deposited protective layer of silicon dioxide having a thickness of about 300 Angstroms, and an O / H top layer of WR4-SF having a thickness of about 150 Angstroms.

[0144] Examples 2-9 below show a comparison of O / H coated mirrors prepared according to this example with mirrors having a conventional protective coating (ie, mirrors lacking an O / H layer).

[0145] Example 2: Wear testing and qualitative tactile evaluation The mirror made according to Example 1 and a conventional mirror lacking an O / H layer were subjected to hardness testing according to military specification MIL-M-13508C, "Mirror, Front Surface Aluminized: For Optical Elements," section 4.4.5. In this test, a 1 pound tester with a 3 / 8" thick pad of cheesecloth is rubbed against the coated surface for 50 passes. Both mirrors met the hardness specification for this test, and neither coating showed any signs of damage after the test.

[0146] Both mirrors were then subjected to the rigorous abrasion test of military specification MIL-C-675C "Coating of Glass Optical Elements (Anti-Reflection)", section 4.5.10. In this more aggressive test, not typically used to evaluate metallic coatings, but only for dielectric coatings, a 2.0 pound tester fitted with an eraser tip was rubbed against the coating surface for 40 passes. Both mirrors failed this more aggressive test, but performed well by the standards of metallic coated mirrors.

[0147] After the abrasion test, the feel of both mirrors was qualitatively evaluated. It was observed that the mirror containing the O / H layer produced according to Example 1 felt noticeably "slicker" than the conventional mirror. Without wishing to be bound by any particular theory, it is believed that this increased "slickness" allows potentially abrasive materials to be deflected away from the mirror surface more easily, thereby protecting the mirror and the O / H coating from scratching.

[0148] Example 3: Adhesion test Several conventional mirrors lacking both an O / H layer and an IAD deposited binder layer were subjected to a "tape pull" adhesion test per MIL-M-13508C, section 4.4.6. In this test, a piece of cellophane tape (Scotch 600) is pressed against the surface and slowly removed at a 90° angle. Some conventional mirrors passed this test while others failed. In contrast, several mirrors with an IAD deposited binder layer (no O / H layer) were tested by the same procedure and all of these mirrors passed.

[0149] The mirrors with the IAD evaporated binder layer, but without the O / H layer, were then subjected to a tape pull adhesion test per MIL-C-675C, section 4.5.12. In this more aggressive test, not typically used to evaluate metallic coatings but reserved for dielectric material coatings, a piece of cellophane tape was pressed against the surface and then the coating was rapidly "snapped off." All mirrors tested passed. The same test protocol was repeated using duct tape, gaffer's tape, electrical tape, packing tape, and Kapton tape in place of the cellophane tape with the same results - none of the tape caused the coating to peel off from the glass substrate of the mirror.

[0150] 5A and 5B, a mirror 200A (FIG. 5A) having an IAD evaporated binder layer but no O / H layer and a mirror 200B (FIG. 5B) made according to Example 1 were subjected to the tape pull adhesion test of MIL-C-675C, section 4.5.12. Both mirrors 200A,B passed the test, although FIG. 5A clearly shows a "tacky" residue 202 remaining on the surface of the mirror 200A without the O / H coating, which required an alcohol wipe to remove.

[0151] In contrast, as shown in FIG. 5B, the O / H treated mirror 200B showed no tape residue and did not require cleaning after testing. Furthermore, it was observed that the tape could be peeled off the O / H treated mirror 200B with little to no force. Thus, this example shows that the addition of an O / H layer to the mirrors 10, 200B of the present disclosure improves the adhesion performance of optical quality mirrors by rejecting external adhesion forces.

[0152] Example 4: Water repellency test The sample mirrors 200A,B shown in Figures 5A and 5B were subjected to a water bead test to evaluate their relative water repellency qualities. Specifically, water droplets were delivered via a pipette to the surfaces of both samples 200A,B. The water droplets applied to both mirrors were of approximately the same volume.

[0153] 6A-7B, there is shown the shape of the water droplet 204 after application to both samples 200A, B. It is readily apparent that the water droplet 204A applied to the mirror 200A without an O / H layer (FIGS. 6A and 7A) is flat and conforms closely to the surface of the mirror 200A, whereas the increased water repellency of the O / H treated mirror 200B (FIGS. 6B and 7B) results in the formation of beads 204B that are in a much closer to spherical conformation.

[0154] As best seen in Figure 7B, the contact angle between the water bead 204B and the surface of the O / H treated mirror 200B is greater than 90° - i.e., rather than resting perpendicular to the surface of the mirror 200B (e.g., in a hemispherical conformation), the bead actually curves under itself. This result is in accordance with the manufacturer's claim that the WR4-SF material can achieve a water contact angle of 116°.

[0155] As shown in Figures 6A and 7A, the water contact angle of uncoated glass and glass with a non-water-repellent coating (e.g., non-O / H treated mirror) is typically about 40°. As a result, the O / H treated mirror 200B only required shaking off the water, whereas the non-O / H treated mirror 200A had to be wiped and dried to remove the water from its surface. Thus, it is believed that the water-repellent phenomenon shown in Figures 6B and 7B is particularly useful for improving the mirror's resistance to extensive wetting, allowing most of the bulk water to simply run off the water-repellent surface of the sheet mirror, with the small remainder being easily removed by wiping, drying, spraying, etc.

[0156] Example 5: Fingerprint attachment and removal test A human test subject placed both thumbs, rubbed together to evenly distribute the sebum, on the surfaces of both sample mirrors 200A and 200B of Example 4, applying approximately equal pressure for approximately equal periods of time.

[0157] 8A and 8B, there are shown fingerprints 206 left behind by placing a tester's thumb on both samples 200A, 200B. While the effect is not as pronounced as the water bead test results of Example 4, the fingerprint 206B left behind on the O / H treated mirror 200B (FIG. 8B) is noticeably less than the fingerprint 206A left behind on the non-O / H treated mirror 200A (FIG. 8A), consistent with the O / H material manufacturer's claim of an oil contact angle of approximately 70°.

[0158] 9A and 9B, both sample mirrors 200A,B were rubbed with a dry paper towel to attempt to remove the fingerprint 206 from the surface. As can be clearly seen, the O / H treated sample mirror 200B (FIG. 9B) has had the fingerprint removed more completely than the non-O / H treated sample mirror 200A (FIG. 9A). Notably, the non-O / H treated mirror 200A was left with a hazy bluish residue that required the application of a foaming spray cleaner to completely remove it. In contrast, the O / H treated sample mirror 200B was free of any residue and did not require the application of any type of cleaner.

[0159] Example 6: Permanent ink removal test 10A and 10B, a Fine-tip Sharpie® permanent marker (Newell Brands, Atlanta, GA) was used to make marks on the surfaces of both sample mirrors 200A,B of Example 4. It is readily apparent that the mirror 200A without an O / H layer (FIG. 10A) readily accepts the permanent ink 208A similar to paper or untreated glass, whereas the increased water and / or oil repellency of the O / H treated mirror 200B (FIG. 10B) causes the surface of mirror 200B to reject the ink 208B, causing the ink to bead up on the surface, resulting in a fainter and lighter mark.

[0160] 11A and 11B, both sample mirrors 200A,B were rubbed with a dry paper towel in an attempt to remove the permanent ink 208 from the surface. As can be clearly seen, the permanent ink 208A deposited on the mirror 200A (FIG. 11A) without the O / H layer was largely unaffected, and it was possible to remove the ink with only the use of foaming spray cleaners and other similar solvents.

[0161] However, this dry wipe with paper towel adequately removed the permanent ink from the O / H treated sample mirror 200B (FIG. 11B). When this test was repeated with the O / H treated sample 200B, it was observed that the permanent ink was generally easiest to remove from the O / H treated sample 200B within a short time after the ink was applied, as the beads of permanent ink were still wet and could be removed with a dry paper towel with little to no pressure. Removal of the permanent ink after drying required the application of some pressure, but removal could still be achieved with a dry paper towel without the use of cleaners or other solvents.

[0162] Example 7: Foaming Spray Cleaner Test An O / H treated mirror 200C with an outer diameter of 150 mm, made according to the procedure of Example 1, was subjected to a cleaning procedure in which a foaming spray glass cleaner was applied to the entire surface of the mirror 200C, and as soon as the foam of the cleaner began to slide across the surface of the mirror 200C, it was wiped off with a dry microfiber mop head. No further pressure was applied to the mop head. This process was continued until the foaming spray glass cleaner was removed from the entire surface of the mirror 200C.

[0163] 12A and 12B, an O / H treated mirror 200C is shown before (FIG. 12A) and after (FIG. 12B) wiping the foaming spray cleaner from the surface. As shown, it is possible to easily apply the foaming spray cleaner to substantially the entire surface of the mirror 200C and then remove the cleaner from the surface by wiping, with no apparent residue of the cleaner, successfully cleaning contaminants from the surface of the mirror 200C as expected. In particular, it was confirmed that the mirror 200C felt "slicker" than a mirror that was not O / H treated upon wiping the cleaner off, as expected. Thus, without wishing to be bound by any particular theory, removal of foaming spray cleaner and similar solvents and / or surfactants from an O / H treated mirror may require less wiping force than a mirror that was not O / H treated, which may protect the mirror from wear and extend its useful life as described herein.

[0164] Example 8: Humidity and Salt Spray Tests Two mirrors 200F,G made according to Example 1 and two conventional mirrors 200D,E lacking an O / H layer were subjected to humidity testing according to MIL-M-13508C, section 4.4.7. In this test, sample mirrors 200D,E,F,G were placed in a specialized cabinet heated to 120°F and humidified to at least about 95% relative humidity for 24 hours. Sample mirrors 200D,E,F,G did not show any type of documented degradation after this test.

[0165] Four sample mirrors 200D, E, F, and G were then subjected to salt spray testing according to ASTM standard B117-73, "Standard Method of Salt Spray (Fog) Testing." In a more aggressive test, not used to evaluate metallic coatings, but only for dielectric material coatings, the sample mirrors were placed in a specialized cabinet heated to 95° F. and exposed to a misted solution of sodium chloride (5%) in water for 24 hours. Conventional optical quality mirrors with protective coatings are generally known to have poor resistance to salt spray, and thus it was desirable to determine whether an O / H coating could overcome this shortcoming and improve the salt spray survivability of optical quality mirrors (as may be important for mirrors that may be exposed to seawater, for example).

[0166] 13A and 13B, the results of the salt spray tests are shown. As is readily apparent, the non-O / H treated sample mirrors 200D,E (FIG. 13A) showed significant degradation over approximately 60-70% of the mirror surface, whereas the O / H treated sample mirrors 200F,G (FIG. 13B) showed degradation over only approximately 5-10% of the mirror surface. In those areas of the O / H treated mirrors 200F,G where there was no visible degradation, the mirror surface remained intact.

[0167] It was also observed that any degradation present on the O / H treated sample mirrors 200F,G appeared only at the edges of the mirrors. The mirrors 200F,G used in this example were fabricated from "snap cut" microscope slides that did not have chamfered edges, and thus, without wishing to be bound by any particular theory, it is hypothesized that the fissures and microcracks on the edges of the samples 200F,G may allow salt water penetration, and that mirrors with chamfered edges and / or that have been treated to minimize edge defects may provide additional resilience to salt spray.

[0168] Example 9: Optical performance test The reflectance of sample mirrors 200A,B of Example 4 was tested over the wavelength range of 400 nm (violet) to 700 nm (red), i.e., over most of the visible spectrum, at an angle of incidence of 20%, with the coatings on both mirrors 200A,B having approximately equal thicknesses. A graph of the reflectance of each sample mirror over this range is shown in Figure 14, with wavelength (in nanometers) on the x-axis and reflectance (in percent) on the y-axis.

[0169] As Figure 14 shows, the application of an O / H layer 160 to the mirror coating has no readily discernible negative or detrimental effect on the optical performance of the mirror coating. In fact, the O / H treated mirror 200B had a slightly higher average reflectance over the range 450-650 nm than the non-O / H treated sample mirror 200A (88.1%), but this difference was within experimental error and was not considered to be a significant difference in performance. This result is expected given that WR4-SF (the O / H coating material applied to O / H treated mirror 200B) is a low absorbing material with a refractive index very similar to that of the material of the protective layer immediately below, i.e., silicon dioxide. Of course, in certain embodiments it may be desirable to select an O / H coating material that alters the optical properties of the mirror to achieve a desired optical effect, and such alterations are expressly contemplated as being within the scope of this disclosure.

[0170] Example 10: Manufacturing Costs The manufacturing process of Example 1 was evaluated for additional time and material costs incurred over a comparative manufacturing process of a conventional mirror without an O / H layer. It was observed that the step of depositing the O / H top layer 160 typically requires approximately 10 minutes of additional time, representing approximately a 25% increase over the conventional non-O / H method, which takes approximately 40 minutes. The resistive tungsten boats that hold the O / H "pills" or "tablets" cost approximately $23 each. Four boats are required for the coating process of Example 1, and each boat is expected to be capable of a total of 10 runs. Thus, the cost per run of the boat is $9.20. The WR4-SF pills cost approximately $23.83 each, with 8 pills being fully consumed in one run. Thus, the cost per run of the O / H materials is $190.64, with a total additional material cost of the O / H coating of $199.84.

[0171] Example 11: Preparation of O / H coated mirror Mirrors for testing the effectiveness of the O / H coatings of the present disclosure were formed by vacuum deposition, specifically by depositing a 700 Angstrom layer of aluminum by high-rate non-IAD vacuum deposition onto a glass substrate, followed by a 1650 Angstrom layer of silicon dioxide on the aluminum layer by argon IAD. Immediately after deposition of the final silicon dioxide layer, an argon ion cleaning step 450 was performed in which the mirror was further bombarded with argon ions without introducing condensed film material, without venting the deposition chamber, as described in conjunction with FIG. 4. The argon ion cleaning was performed for approximately 15 minutes to remove contaminants and improve the uniformity of the mirror surface (i.e., to "smooth" the mirror surface, reducing roughness) prior to application of the O / H coating.

[0172] Immediately after the argon ion flush, and still without venting the deposition chamber, two tungsten boats (RD Mathis Company, Signal Hill, CA) were placed into the resistance source of the S36 coating chamber. Two "pills" or "tablets" of O / H coating material, specifically Surfclear 300 (Canon Optron, Inc., Yuki, Japan), were then added to each boat. The O / H material was then deposited onto the final silicon dioxide layer 140 by vacuum evaporation to form a finished optical quality mirror with an energetically coupled O / H coating.

[0173] The completed mirror coating included (in ascending order from substrate 110) a binder layer 120 of aluminum metal having a thickness of about 250 Angstroms (applied at a low deposition rate), a reflective layer 130 of aluminum metal having a thickness of about 700 Angstroms (applied at a high deposition rate), an IAD deposited first protective layer 140 of silicon dioxide having a thickness of about 1350 Angstroms, a non-IAD deposited second protective layer 150 of silicon dioxide having a thickness of about 300 Angstroms, and an O / H top layer 160 of Surfclear 300 having a thickness of about 150 Angstroms.

[0174] The following Examples 12-18 show a comparison of O / H coated mirrors prepared according to this Example 11 with mirrors having a conventional protective coating (ie, lacking an O / H layer).

[0175] Example 12: Wear Testing and Qualitative Tactile Evaluation The mirror made according to Example 11 and a conventional mirror lacking an O / H layer were subjected to hardness testing per military specification MIL-M-13508C, section 4.4.5, "Mirror, Front Surface Aluminized: For Optical Elements." In this test, a 1 pound tester containing a 3 / 8" thick pad of cheesecloth is rubbed against the coated surface for 50 passes. Both mirrors met the hardness specification for this test, and neither coating showed any signs of damage after the test.

[0176] Both mirrors were then subjected to the rigorous abrasion test of Military Specification MIL-C-675C, Section 4.5.10, "Coating of Glass Optical Elements (Anti-Reflection)." In this more aggressive test, not typically used to evaluate metallic coatings, only dielectric coatings, a 2.0 pound tester fitted with an eraser tip was rubbed against the coating surface for 40 passes. Both mirrors failed this more aggressive test, but performed well by the standards for metal coated mirrors.

[0177] After the abrasion tests, the feel of both mirrors was qualitatively evaluated. It was determined that the mirror including the O / H layer felt noticeably "slippery" to the touch compared to the conventional mirror. Without wishing to be bound to any particular theory, it is believed that this increased "slipperiness" allows potentially abrasive materials to be more easily deflected away from the mirror surface, thereby protecting the mirror and O / H coating 160 from scratches.

[0178] Example 13: Adhesion test Several conventional mirrors lacking both the O / H layer and the IAD deposited binder layer were subjected to the "tape pull" adhesion test per MIL-M-13508C, section 4.4.6, in which cellophane tape (Scotch 600) is pressed against the surface and slowly peeled off at a 90° angle. Some conventional mirrors passed this test while others failed. In contrast, several mirrors with an IAD deposited binder layer (no O / H layer) were also tested by the same procedure, and all of these passed.

[0179] The mirrors with the IAD deposited binder layer, but without the O / H layer, were then subjected to a tape pull adhesion test per MIL-C-675C, section 4.5.12. In this more aggressive test, not typically used to evaluate metallic coatings, but reserved for dielectric material coatings, a piece of cellophane tape was pressed against the surface and then the coating was rapidly "peeled off." All mirrors tested passed. The same test protocol was repeated using duct tape, gaffer's tape, electrical tape, packing tape, and Kapton tape in place of the cellophane tape with the same results - none of the tape caused the coating to peel away from the glass substrate of the mirror.

[0180] 15A and 15B, mirror 210A (FIG. 15A) and mirror 210B (FIG. 15B) made according to Example 11, having an IAD evaporated binder layer 120 but no O / H layer, were subjected to the tape pull adhesion test of MIL-C-675C, section 4.5.12. Both mirrors 210A,B passed the test, although FIG. 15A clearly shows a "tacky" residue 202 remaining on the surface of mirror 210A without the O / H coating, which required an alcohol wipe to remove.

[0181] In contrast, as shown in FIG. 15B, the O / H treated mirror 210B showed no tape residue and did not require cleaning after testing. Furthermore, it was observed that the tape could be peeled off the O / H treated mirror 210B with little to no force. Thus, this example shows that the addition of an O / H layer to the mirror 10, 210B of the present disclosure improves the adhesion performance of optical quality mirrors by rejecting external adhesion forces.

[0182] Example 14: Water repellency test The sample mirrors 210A,B shown in Figures 15A and 15B were subjected to a water beading test to evaluate their relative water repellency qualities. Specifically, droplets of water 204 were delivered via pipette to the surfaces of both mirrors 210A,B. The droplets applied to both mirrors were of approximately the same volume.

[0183] 16A-17B, there is shown the shape of the water droplet 204 after application to both sample mirrors 210A, B. It is readily apparent that the water droplet 204A applied to the mirror 210A without an O / H layer (FIGS. 16A and 17A) is flat and conforms closely to the surface of the mirror 210A, whereas the increased water repellency of the O / H treated mirror 210B (FIGS. 16B and 17B) results in the formation of beads 204B that are in a much closer to spherical conformation.

[0184] As best seen in Figure 17B, the contact angle between the water bead 204B and the surface of the O / H treated mirror 210B is greater than 90° - i.e., rather than resting perpendicular to the surface of the mirror 210B (e.g., in a hemispherical conformation), the bead actually curves back under itself. This result is in accordance with the manufacturer's claim that the "Surfclear 300" material can achieve a water contact angle of 115°.

[0185] 16A and 17A, the water contact angle of uncoated glass and glass with a non-hydrophobic coating (e.g., non-O / H treated mirror 210A) is typically about 40°. As a result, the non-O / H treated mirror 210A had to be wiped and dried to remove the surface water, whereas the O / H treated mirror 210B only required shaking off the water.

[0186] The two sample mirrors 210A,B were then tested to evaluate the "sliding angle," i.e., the angle at which the water bead begins to "slide" (i.e., flow) off the sample when the sample is tilted. For the mirror 210A without O / H treatment (FIGS. 16A, 17A), the sliding angle was about 85°, and flow did not begin unless the sample mirror 210A was held nearly vertical, and even under this condition the flow was slow and residual water remained on the surface and had to be wiped off.

[0187] In contrast, the O / H treated mirror 210B (FIGS. 16B, 17B) had a sliding angle of only about 14°, and even at low angles the water flowed quickly and completely off the mirror 210B, leaving the mirror 210B dry without the need to wipe off any residual water. Thus, the water repellency phenomenon illustrated in FIGs. 16B and 17B may be particularly useful in improving the resilience of the mirrors 10, 210B of the present disclosure to large scale wetting events, as most or perhaps even all of the desired bulk water would simply flow or roll off the water repellent surface of the sheet mirror.

[0188] Example 15: Fingerprint attachment and removal test A human test subject placed the thumbs of both hands, which had been rubbed together to distribute the sebum evenly, against the surfaces of both sample mirrors 210A and 210B of Example 14, applying approximately equal pressure for approximately equal periods of time.

[0189] 18A and 18B, there are shown fingerprints 206 left by placing a tester's thumb on both sample mirrors 210A, 210B. While the effect is not as pronounced as the water bead test results in Example 14, the fingerprint 206B left on the O / H treated mirror 210B (FIG. 18B) is noticeably less than the fingerprint 206A left on the non-O / H treated mirror 210A (FIG. 18A), consistent with the O / H material manufacturer's claim of an oil contact angle of approximately 70°.

[0190] 19A and 19B, both sample mirrors 210A,B were rubbed with a dry paper towel in an attempt to remove the fingerprints 206 from the mirror surface. As can be clearly seen, the fingerprints were removed much more completely from the O / H treated mirror 210B (FIG. 19B) than from the non-O / H treated mirror 210A (FIG. 19B). In particular, the non-O / H treated mirror 210A left a hazy bluish residue that required the application of a foaming spray cleaner to completely remove it. In contrast (in contract), the O / H treated mirror 210B was residue-free and did not require the application of any type of cleaner, as shown in FIG. 19B.

[0191] Example 16: Permanent ink removal test 20A and 20B, a Fine-tip Sharpie® permanent marker (Newell Brands, Atlanta, GA) was used to make marks on the surfaces of both sample mirrors 210A,B of Example 14. The mirror 210A (FIG. 20A) without an O / H layer appears to readily accept the permanent ink 208A as readily as paper or untreated glass. In contrast, the increased water and / or oil repellency of the O / H treated mirror 210B (FIG. 20B) causes the surface of the mirror 210B to reject the ink 208B, causing the ink to bead up on the surface, resulting in a fainter and lighter mark.

[0192] 21A and 21B, both sample mirrors 210A,B were rubbed with a dry paper towel in an attempt to remove the permanent ink 208 from their surfaces. As can be clearly seen, the permanent ink 208A deposited on the mirror 210A without the O / H layer (FIG. 21A) was largely unaffected and the ink could be removed with only the use of a solvent such as a foaming spray cleaner. However, as shown in FIG. 21B, this dry wipe with the paper towel sufficiently removed the permanent ink from the O / H treated mirror 210B. When this test was repeated with the O / H treated sample 210B, it was observed that the permanent ink was generally easiest to remove from the O / H treated sample 210B within a short time of ink application, as the beads of permanent ink were still wet and could be removed with a dry paper towel with little pressure. Removal of the permanent ink after drying required the application of some pressure, but removal could still be achieved with a dry paper towel without the use of a cleaner or other solvent.

[0193] Example 17: Uniformity of O / H Coating Application To test the uniformity of application of the O / H coating to a mirror having a radius of curvature of approximately 9.25 feet, sample mirrors 210C-1, 210C-2, 210C-3, 210C-4, 210C-5, 210C-6, and 210C-7 were spaced along the surface of a surrogate substrate having a radius of curvature of approximately 9.25 feet and fabricated according to Example 11. Sample mirrors 210C-1 through 210C-7 were positioned approximately every 10 inches along a radius starting from the center of the surrogate substrate as fabricated. Sample mirrors 210C-1 through 210C-7 were then marked with the same marker used in Example 16. These radial points represent concentric circles on the front surface 14 of mirror 10 because the surrogate and substrate rotate about the center of the substrate while in the deposition chamber during the coating process.

[0194] 22, the effect of the ink 208 from the permanent marker is shown to be consistent on each of the sample mirrors 210C-1 through 210C-7 positioned along the radial length of the surrogate substrate, indicating that the effect of the O / H coating is effectively uniformed across the entire width of the substrate.

[0195] Example 18: Foaming Spray Cleaner Test The O / H treated mirror with 11 ft radius of curvature made by the procedure of Example 11 was subjected to a cleaning procedure in which foaming spray glass cleaner was applied to the entire surface of the mirror, and then wiped with a dry microfiber mop head as soon as the foam of cleaner started to slide on the surface of the mirror. No further pressure was applied to the mop head. This process was continued until the foaming spray glass cleaner was removed from the entire surface of the mirror. The results were the same as those described in Example 7.

[0196] Example 19: Optical performance test The reflectance of sample mirrors 210A, 210B of Example 14 was tested over the wavelength range of 400 nm (violet) to 700 nm (red), i.e., over most of the visible spectrum, at an angle of incidence of 20%, with the coatings on both mirrors having approximately the same thickness. A graph of the reflectance of each mirror 210A, 210B over this range is provided as Figure 23 (wavelength in nanometers is on the x-axis, percent reflectance is on the y-axis).

[0197] As Figure 23 shows, the application of the O / H layer 160 to the mirror coating has no readily discernible negative or detrimental effect on the optical performance of the mirror coating. This result is expected since Surfclear 300 (the O / H coating material applied to the O / H treated mirror 210B) is a low absorption material with a refractive index very similar to that of the material of the protective layer immediately below, i.e., silicon dioxide of protective layer 140. Of course, in certain embodiments it may be desirable to select the O / H coating material to modify the optical properties of the mirror to achieve a desired optical effect, and such modifications are expressly contemplated as being within the scope of this disclosure.

[0198] To test the optical uniformity of O / H coating 160, this test was repeated with seven sample mirrors 210C-1 through 210C-7 fabricated as described in Example 17. Referring now to Figures 24A-G, the reflectance of mirrors 210C-1 through 210C-7 at each radial point is graphed as a separate curve (seven graphs total) with wavelength (in nanometers) on the x-axis and percent reflectance on the y-axis. More specifically, FIG. 24A shows the reflectivity of mirror 210C-1 formed while positioned at the center of the surrogate substrate (or r=0"). FIG. 24B shows the reflectivity of mirror 210C-2 formed approximately 10" (or r=10") from the center of the surrogate substrate. FIG. 24C shows the reflectivity of mirror 210C-3 formed approximately 20" (or r=20") from the center of the surrogate substrate. FIG. 24D shows the reflectivity of mirror 210C-4 formed approximately 30" (or r=30") from the center of the surrogate substrate. FIG. 24E shows the reflectivity of mirror 210C-5 formed approximately 30" (or r=30") from the center of the surrogate substrate when formed. FIG. 24F shows the reflectivity of mirror 210C-5, positioned approximately 40" (or r=40") from the center of the surrogate substrate. FIG. 24F shows the reflectivity of mirror 210C-6, positioned approximately 50" (or r=50") from the center of the surrogate substrate. FIG. 24G shows the reflectivity of mirror 210C-7, positioned approximately 60" (or r=60") from the center of the surrogate substrate. Optical performance was shown to be broadly consistent for mirrors formed at all points along the radial length of the surrogate substrate, with only negligible changes in reflectivity as a function of radial distance.

[0199] Example 20: Coating thickness uniformity To determine the thickness of O / H coating 160 at each of the seven radii represented by sample mirrors 210C-1-210C-7 of Example 17, the reflectance peak values ​​of each curve shown in Figures 24A-24G were determined, and then each of these peak reflectance values ​​was compared to the average reflectance value of all seven peaks. This method produces a "normalized thickness" value that represents the uniformity of the coating.

[0200] Referring now to FIG. 25, the normalized thickness for all seven radius points is shown; "#1" shows the normalized thickness at radius 0" (sample mirror 210C-1 was placed on the surrogate substrate in the deposition chamber at the center of the surrogate substrate) and "#7" shows the normalized thickness for sample mirror 210C-7 placed at radius 60" of the surrogate substrate. As FIG. 25 shows, the largest variations from the average thickness coating (normalized to 1.000 in this case) were at points #4 (mirror 210C-4) and #7 (mirror 210C-7), with normalized thicknesses of about 0.987 and about 1.013, respectively. In other words, at all measurement points, the coating thickness was within about ±1.3% of the average coating thickness. This is well within the ±5% specification for many high performance mirror applications and is comparable to O / H coated mirrors manufactured by conventional methods.

[0201] Example 21: Manufacturing Costs The additional time and material costs incurred in the manufacturing process of Example 11 versus a comparative manufacturing process of a conventional mirror without an O / H layer were evaluated. It was observed that the steps of performing an argon ion rinse (operation 450 of method 400) and depositing the O / H top layer 160 (operation 460 of method 400) typically take about an additional 20 minutes, representing about a 50% increase over the conventional non-O / H method, which takes about 40 minutes. The resistive tungsten boats that hold the O / H "pills" or "tablets" have a cost of about $12.47 each. Two boats are required for the coating process of Example 11, and each boat is expected to be capable of a total of three manufacturing runs. Thus, the cost per boat run is $8.31. Surfclear 300 has a cost of about $48.25 each, with all four pills consumed in each manufacturing run. Thus, the cost per O / H material is $193.00, with a total additional material cost for the O / H coating of $201.31.

[0202] Example 22: O / H coating of damaged mirror A conventional circular mirror 210D having a radius of curvature of 11 feet, which was severely damaged during the grinding and polishing process and had large grooves in the uncoated mirror surface, was coated with an O / H layer 160 by the method 400 of FIG. 4 described in Example 11. This mirror 210D was then subjected to the tests described in Examples 12-16 and 18 with substantially identical results. FIG. 26 shows the permanent ink test results, showing the ink 208 on the mirror 210D. FIG. 27 shows the water 204 from the water application test on the mirror. The mirror 210D was then exposed to ambient chamber conditions for 52 days with no visible degradation or other negative effect on the effectiveness of the O / H coating.

[0203] The disclosure illustratively disclosed herein may suitably be practiced in the absence of any element not specifically disclosed herein, however, it will be apparent to those skilled in the art that numerous changes, variations, modifications, other uses and applications of the disclosure are possible, and that changes, variations, modifications, other uses and applications that do not depart from the spirit and scope of the disclosure are deemed to be covered by the disclosure, which is limited only by the claims that follow.

[0204] The foregoing discussion of the present disclosure has been presented for purposes of illustration and description. The foregoing is not intended to limit the disclosure to the form disclosed herein. In the foregoing detailed description, for example, various features of the present disclosure have been grouped together in one or more embodiments for the purpose of streamlining the disclosure. Features of the embodiments of the present disclosure may be combined in alternative embodiments other than those described above. This method of disclosure is not to be interpreted as reflecting an intention that the claimed invention requires more features than are expressly recited in each claim. Rather, as the following claims reflect, inventive aspects lie in less than all features of a single such disclosed embodiment. Thus, the following claims are hereby incorporated into this detailed description, with each claim standing on its own as a separate preferred embodiment of the present invention.

[0205] Further, while this specification includes a description of one or more embodiments and certain variations and modifications, other variations, combinations, and modifications are within the scope of the disclosure, for example, as would be within the skill and knowledge of one of ordinary skill in the art after appreciating the disclosure. The invention is intended to be entitled to include alternative embodiments, including alternative, interchangeable, and / or equivalent structures, functions, ranges, or steps to those set forth in the claims, whether or not such alternative, interchangeable, and / or equivalent structures, functions, ranges, or steps are disclosed herein, without any intention to dedicate any patentable subject matter to the public.

Claims

1. (a) applying a binder layer comprising aluminum metal to a substrate at a rate of 5 angstroms / second or less; (b) applying a reflective layer comprising aluminum metal onto the binder layer at a rate of at least 15 angstroms / second; (c) applying a protective layer comprising silicon dioxide over the reflective layer to form an uncoated optical mirror; (d) applying a top layer over the protective layer to form a coated optical mirror; Including, A method for producing a coated optical mirror, wherein the top layer is at least one of oil-repellent and water-repellent.

2. The method of claim 1 , wherein at least one of the binder layer and the protective layer is deposited by ion-assisted deposition.

3. (i) the thickness of the binder layer is 50 angstroms to 450 angstroms; (ii) the thickness of the reflective layer is between 500 angstroms and 900 angstroms; (iii) the thickness of the protective layer is between 950 angstroms and 2350 angstroms; and (iv) the thickness of the top layer is between 100 angstroms and 300 angstroms; The method of claim 1 , wherein at least one of the following is true:

4. 10. The method of claim 1, wherein the combined thickness of the binder layer, reflective layer, protective layer and top layer varies by no more than 2% over the area of ​​the optical mirror.

5. 10. The method of claim 1, wherein the oil / water repellent material of the top layer is selected from the group consisting of Substance WR4-SF Patinal®, Surfclear 100, and Surfclear 300.

6. 10. The method of claim 1, wherein the vacuum chamber in which steps (c) and (d) are performed is not purged or vented between steps (c) and (d).

7. The method of claim 1 , wherein the reflective layer is deposited by a vacuum evaporation aluminum silver plating process.

8. 10. The method of claim 1, wherein the time interval between steps (c) and (d) is 60 minutes or less.

9. The method of claim 1 , wherein the substrate is formed of glass.

10. The method of claim 1 , wherein the substrate is formed of a plastic, metal, or polymer.

11. The method of claim 1 , wherein the coated optical mirror includes a front surface that is concave.

12. 10. The method of claim 1, further comprising ion cleaning the uncoated optical mirror between steps (c) and (d).

13. The method of claim 1 , wherein the protective layer is a first protective layer, and the method further comprises applying a second protective layer located between the first protective layer and the top layer.

14. 10. The method of claim 1, wherein the rate of step (a) is between 0.1 Angstroms / second and 5.0 Angstroms / second.

15. 10. The method of claim 1, wherein the rate of step (b) is from 15 Angstroms / second to 50 Angstroms / second.

16. The method of claim 1 , wherein the protective layer is deposited on the reflective layer by ion-assisted deposition.

17. The method of claim 1 , wherein the top layer is deposited by ion-assisted deposition.

18. The method of claim 1 , further comprising bonding or interconnecting the substrate to a mirror body.

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