Corrosion resistant solar mirror

WO 2012/078227 PCT/US2011/052244

CORROSION RESISTANT SOLAR MIRROR

NOTICE OF GOVERNMENT SUPPORT

[0001] This invention was made with Government support under Government Contract No. DE-FC36-08GO18033 (DOE Solar Power) awarded by the U.S. Department of Energy. The United States Government may have certain rights in this invention. CROSS-REFERENCE TO RELATED APPLICATIONS [0002] This application Is related to and claims the benefits of U. S. Applications Serial Nos. 12/330,580; 12/330,618; and 12/330,651, all filed on December 9, 2008 and all of which are herein incorporated by reference.

BACKGROUND OF THE INVENTION 1. Field of the Invention [0003] This invention relates generally to solar mirrors and, in one particular embodiment, to a solar mirror having improved anticorrosion properties for the metallic layer of the mirror, 2. Technical Considerations [0004] With the increasing costs of fossil-based fuels, solar power is becoming a more commercially acceptable and economically viable source of energy. One known application is using mirrors to concentrate solar power for electrical generation. Mirrors having high reflectance of solar radiation are used for "concentrated solar thermal power" (CSTP) installations. One conventional system uses curved parabolic solar mirrors to concentrate solar energy onto tubes positioned along a focal line. A heat transfer medium in the tubes carries the absorbed heat energy to a generator station where it is used for power generation, Another conventional system uses a solar tower in which a number of fiat solar mirrors direct solar energy at a particular location on ihe tower. The heat generated by the focused solar energy is transferred to a working fluid, such as sodium, and the heated working fluid is used for power generation. A further application of such mirrors is for "concentrated photovoltaics" (CPV). in this application, mirrors focus or concentrate solar energy onto high-efficiency photovoltaic (PV) devices, thereby improving the energy output per device.

[0005] In these systems, it is desirable that the mirrors reflect as much solar energy as possible. It Is also desirable that the mirrors have as long a commercial life as possible to preclude frequent changing of the mirrors.

[0006] Conventional solar mirrors utilize a reflective metaf layer to reflect the solar energy. These mirrors are positioned outdoors in an array that can include hundreds or 1 WO 2012/078227 PCT/US2011/052244 thousands of mirrors. Since the mirrors are exposed to environmental conditions» such as rain, snow, airborne contaminants, etc., a problem with these conventional solar mirrors is that the reflective metal layer can become corroded or degraded by attack from moisture or airborne contaminants. Some solar mirrors include a casing or backing to help keep out such materials. However, with age and wear, the backings can crack or break, allowing moisture to enter and corrode the meta! layer. This corrosion decreases the reflectance of the mirror and shortens the commercial life of the mirror.

[0007] Therefore, it would be advantageous to provide a reflective article, such as a solar mirror, with increased resistance to corrosion.

SUMMARY OF THE iNVENTiON

[00081 A reflective article comprises a substrate having a first major surface and a second major surface. A primary reflective coating comprising at least one meta I lie layer is formed over at least a portion of a major surface of the substrate. An anode, such as a sacrificial anode, is in electrical contact with the metallic layer of the primary reflective coating. The anode can comprise a material having a greater oxidation potential than the metallic layer.

[0009] A further reflective article comprises a substrate having a first major surface and a second major surface. A primary reflective coating comprising at least one metallic layer is formed over at least a portion of a major surface of the substrate. A source of electrons, such as a battery, solar cell, or similar source of electrical potential, is in electrical contact with the metallic layer of the primary reflective coating.

[0010] Another reflective article comprises a transparent substrate having a first major surface and a second major surface. A base coat is formed over at ieast a portion of the second major surface. A primary reflective coating comprising at least one metallic layer is formed over at least a portion of the base coat. A protective coating is formed over at least a portion of the primary reflective coating. The article further comprises a source of electrons, such as a solar cell and/or a battery, and an anode, with the source of electrons connected to the metallic layer and the anode.

BRIEF DESCRIPTION OF THE DRAWINGS

[0011] The invention will be described with reference to the following drawing figures wherein like reference numbers identify like parts throughout.

[0012] Fig. 1A is a side, sectional view (not to scale) of a reflective article incorporating features of the invention; [0013] Fig. 1B is a side, sectional view (not to scale) of another reflective article incorporating features of the invention; 2 WO 2012/078227 PCT/US2011/052244 [0014] Fig, 1C is a side, sectional view (not to scale) of a further reflective article incorporating features of the invention; [0015] Fig. 2 is a side, sectional view (not to scale) of another reflective article of the invention; [0016] Fig. 3 is a side, sectional view (not to scale) of a further reflective article of the invention; [0017] Fig. 4 Is a side, sectional view (not to scale) of an additional reflective article of the invention; [0018] Fig. 5 is a side view (not to scale) of a reflective article of the invention attached to a base; [0019] Fig. 6 is a side view (not to scale) of a reflective article having a passive corrosion reducing assembly; [0020] Fig. 7 is a schematic view of an active corrosion reducing assembly for a reflective article; [0021] Fig 8 Is a front view (not to scale) of a reflective article incorporating an active corrosion assembly; and [0022] Fig, 9 is a side, sectional view (not to scale) of the reflective article of Fig. 8 taken along the line IX-IX of Fig. 8. DESCRIPTION OF THE PREFERRED EMBODIMENTS [0023] As used herein, spatial or directional terms, such as "left", "right”, "inner’', "outer”, "above”, "below”, and the like, relate to the invention as it is shown in the drawing figures. However, it is to be understood that the invention can assume various alternative orientations and, accordingly, such terms are not to be considered as limiting. Further, as used herein, all numbers expressing dimensions, physical characteristics, processing parameters, quantities of ingredients, reaction conditions, and the like, used in the specification and claims are to be understood as being modified in all instances by the term "about”. Accordingly, unless indicated to the contrary, the numerical values set forth in the following specification and claims may vary depending upon the desired properties sought to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical value should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Moreover, ail ranges disclosed herein are to be understood to encompass the beginning and ending range values and any and all subranges subsumed therein. For example, a stated range of "1 to 10” should be considered to include any and all subranges between (and inclusive of) the minimum value of 1 and the maximum vaiue of 10; that is, ail subranges beginning with a minimum value of 1 or more and ending 3 WO 2012/078227 PCT/US2011/052244 with a maximum value of 10 or less, e.g., 1 to 3.3, 4.7 to 7.5, 5.5 to 10, and the like. Further, as used herein, the terms “formed over”, "deposited over” or "provided over" mean formed, deposited, or provided on but not necessarily in direct contact with the surface. For example, a coating layer “formed over” a substrate does not preclude the presence of one or more other coating layers or films of the same or different composition located between the formed coating layer and the substrate. As used herein, the terms "polymer" or "polymeric” include oligomers, homopolymers, copolymers, and terpoiymers, e.g., polymers formed from two or more types of monomers or polymers. The terms "visible region” or "visible light" refer to electromagnetic radiation having a wavelength in the range of 380 nm to 780 nm. The terms "infrared region” or "infrared radiation" refer to electromagnetic radiation having a wavelength In the range of greater than 780 nm to 100,000 nm. The terms “ultraviolet region” or “ultraviolet radiation” mean electromagnetic energy having a wavelength in the range of 100 nm to less than 380 nm. Additionally, all documents, such as but not limited to issued patents and patent applications, referred to herein are to be considered to be "incorporated by reference” in their entirety. Also, parameters such as “visible transmission” and "visible reflection” and the like are those determined using conventional methods.

Those skilled in the art will understand that properties such as visible transmission or visible reflection can vary based on the physical dimensions, e.g,, thickness, of the article being tested. Therefore, any comparison to the present invention should be calculated at an equivalent thickness.

[0024] For purposes of the following discussion, the invention will be discussed with reference to use with a reflective article to reflect electromagnetic radiation, such as but not limited to a solar mirror to reflect electromagnetic soiar radiation. As used herein, the term "solar mirror” refers to any article configured to reflect electromagnetic soiar radiation, such as visible and/or infrared and/or ultraviolet radiation, e.g., for use in concentrated solar power systems. However, it is to be understood that the invention Is not limited to use with solar mirrors but could be practiced with articles in other fields, such as but not limited to laminated or non-Iaminated residential and/or commercial mirrors, or reflectors for high-performance optical systems {e.g., video projectors or optical scanners), just to name a few. Therefore, it is to be understood that the specifically disclosed exemplary embodiments are presented simply to explain the general concepts of the invention and that the invention is not limited to these specific exemplary embodiments.

[0Θ25] In one aspect, the reflective article of the invention comprises at least some of the following components: (1) a light-transmitting substrate or superstrata having low absorption of solar radiation in the region(s) of the electromagnetic spectrum that it is desirable for the article to reflect, (2) one or more primary reflective layer(s) having high reflectivity of soiar radiation in the region(s) of the electromagnetic spectrum that is desirable 4 WO 2012/078227 PCT/US2011/052244 to be reflected, (3) optional "primer” or "blocker” or "barrier” layer(s) which can help preserve the reflective properties of the reflective layer(s) and/or improve the adhesion of adjacent components, (4) one or more optional secondary reflective layers such as additional metal, semiconductor, dielectric, and/or composite layers which can enhance the reflectivity of the article over some or all of the desired wavelength range and/or serve to protect the primary reflective layer(s) and/or serve to prevent diffusion of chemical species between layers and/or substrates/superstrates, (5) optional corrosion-inhibiting layer(s), (Q) optional sacrificial iayerfs) comprising materials which exhibit greater propensity to corrode than the materials comprising components 2, 3, and/or 4, (7) optional layer(s) of materials (e.g. metal or metal alloys) which are corrosion-resistant and/or form passivation layers that prevent chemically-reactive environmental species from interaciing/reacting with other components, (8) optional encapsulation layer(s) which protect underlying layers (especially reflective layer(s)) from attack by environmental hazards (e.g. atmospheric pollutants, water, mechanical hazards), (9) optional adhesive layer(s) which bond the article to optional underlying lamina/plies/substrates/superstrates or other supporting structures, (10) optional polymeric layer(s), (11) optional additional lamina/piles/substrates/superstrates, (12) optional iow-maintenance (e.g. hydrophtllic and/or photocata lytic or hydrophobic) top surface, and (13) optional edge sealants.

[0026] A non-limiting reflective article Incorporating features of the invention is illustrated in Fig. 1A and will be described herein as a solar mirror 1. The solar mirror 1 can have any desired reflectance or transmittance in the region(s) of interest within the electromagnetic spectrum (e.g., ultraviolet, visible, near infrared, far infrared, microwave, radiowave, etc.). For example, the solar mirror 1 can have a visible light reflection at a wavelength of 550 nm of at least 85 %, such as at least 90 %, such as at least 95 %.

[0027] In the embodiment illustrated in Fig. 1A, the solar mirror 1 includes a substrate or ply 12 with a first major surface 14, i.e. an outer major surface, and an opposed second major surface 16, i.e. an inner major surface, in the following discussion, the first major surface 14 faces the incident radiation and the second surface 16 faces opposite the direction of the incident radiation. An optional basecoat 102 can be provided over at least a portion of one of the major surfaces, such as the second major surface 16. In illustrated non-limiting embodiment, a primary reflective coating 22 is formed over at least a portion of the second major surface 16, e.g. over at least a portion of the basecoat 102, if present. A protective coating 50 is provided over at least a portion of the primary reflective coating 22. While in the illustrated embodiment the coatings are formed over the second major surface 16, it is understood that at least some of the coatings could alternatively be formed over the first major surface 14. 5 WO 2012/078227 FCT/US2011/052244 [0028] in the broad practice of the invention, the ply 12 can include any desired material having any desired characteristics. For example, the ply 12 can be transparent or translucent to visible light By “transparent" is meant having a transmission of greater than 0% up to 100% in a desired wavelength range, such as visible light. Alternatively, the piy 12 can be translucent. By “translucent'’ is meant allowing electromagnetic radiation (e.g., visible light) to be transmitted but diffusing or scattering this radiation. Examples of suitable materials for the piy 12 include, but are not limited to, thermoplastic, fhermoset, or elastomeric polymeric materials, glasses, ceramics, and metals or metal alloys, and combinations, composites, or mixtures thereof. Specific examples of suitable materials include, but are not limited to, plastic substrates (such as acrylic polymers, such as poiyacrylates; poiyalky[methacrylates, such as polymethylmethacrylates, polyethyimethacryiates, polypropylmethacrylates, and the like; polyurethanes; polycarbonates; polyalkylte re phthalates, such as polyethyleneterephthalate (PET), polyp ropylenetere phthalates, polybutyleneterephthalates, and the like; polysiloxane-containing polymers; or copolymers of any monomers for preparing these, or any mixtures thereof); ceramic substrates; glass substrates; or mixtures or combinations of any of the above. For example, the piy 12 can include conventional soda-lime-siiicate glass, borosilicate glass, or leaded glass. The glass can be clear glass. By “clear glass" is meant non-tirsted or non-colored glass. Alternatively, the glass can be tinted or otherwise colored glass. The glass can be annealed or heat-treated glass. As used herein, the term "heat treated" means tempered, bent, heat strengthened, or laminated. The glass can be of any type, such as conventional float glass, and can be of any composition having any optical properties, e.g., any value of visible transmission, ultraviolet transmission, infrared transmission, and/or total solar energy transmission. The ply 12 can be, for example, clear float glass or can be tinted or colored glass. Although not limiting to the invention, examples of glass suitable for the ply 12 are described in U.S. Patent Nos. 4,746,347; 4,792,536; 5,030,593; 5,030,594; 5,240,886; 5,385,872; and 5,393,593. The piy 12 can be of any desired dimensions, e.g,, length, width, shape, or thickness, in one exemplary embodiment, the first ply 12 can be greater than OuptolOmm thick, such as 1 mm to 10 mm thick, e.g., 1 mm to 5 mm thick, e.g,, less than 4 mm thick, e.g., 3 mm to 3.5 mm thick, e.g., 3.2 mm thick. Additionally, the ply 12 can be of any desired shape, such as flat, curved, parabolic-shaped, or the like. Also, when the primary reflective layer(s) 22 reside on the second major surface 16 of the article, the ply 12 can comprise one or more materials that exhibit low absorption of electromagnetic radiation in the region(s) of electromagnetic radiation desired to be reflected.

[0029] In one non-limiting embodiment, the ply 12 can have a high visible light transmission at a reference wavelength of 550 nanometers (nm) and a reference thickness 6 WO 2012/078227 PCT/US201J/052244 of 3,2 mm. By “high visible light transmission" is meant visible light transmission at 550 nm of greater than or equal to 85%, such as greater than or equal to 87%, such as greater than or equa! to 90%, such as greater than or equal to 91%, such as greater than or equal to 92%, such as greater than or equal to 93%, such as greater than or equal to 95%, at 3,2 mm reference thickness for the ply. Particularly useful glass for the practice of the invention is disclosed in U.S. Patent Nos. 5,030,593 and 5,030,594. Non-limiting examples of glass that can be used for the practice of the invention include, but are not limited to, Starphire®, Solarphire®, Solarphire® PV, Solargreen®, Sotextra®, GL-20®, GL-35™, Solarbronze®, CLEAR, and Solargray® glass, all commercially available from PPG Industries Inc. of Pittsburgh, Pennsylvania.

[0030] The basecoat 102 can provide a stronger or more durable interface between the ply 12 and the primary reflective coating 22. The basecoat 102 can comprise one or more materials chosen such that the interface between the basecoat 102 and the primary reflective coating 22 is more mechanically, chemically, and/or environmentally stable than an interface between the ply 12 and the primary reflective layer 22. Also, the basecoat 102 can serve as a diffusion barrier to the elemental exchange between the ply 12 and the primary reflective coating 22 (such as the migration of sodium out of the glass substrate into the overlying coating(s) or the migration of metal, e.g., stiver, from the primary reflective coating 22 to the glass), especially as might occur as the result of subjecting the coated article to elevated temperatures, for example, for bending or heat strengthening. Additionally or alternatively, the basecoat 102 can provide a smoother or more planar surface upon which to deposit an overlaying coating, e.g., the primary reflective coating 22. Examples of materials suitable for the basecoat 102 include, but are not limited to, inorganic materials such as but not limited to transparent low absorption dielectrics, such as metal oxides or combinations, composites, or mixtures of metai oxides. Examples of suitable metal oxides include alumina, titania, zirconia, zinc oxide, zinc stannate, tin oxide, or mixtures or combinations thereof. Other examples for the basecoat 102 include one or more layers of silicon dioxide and/or silicon nitride. In one non-limiting embodiment, the basecoat 102 comprises titania. The basecoat 102 can have any composition or thickness to provide sufficient functionality to the article (e.g,, mechanical, chemical, passivation, planarization, adhesion, diffusion barrier properties, environmental durability enhancement, optical, and the like). In one particular embodiment where the basecoat 102 is titania, the basecoat 102 has a thickness in the range of 0.1 nm to 5 nm, such as 0.1 nm to 3 nm, such as 0.5 nm to 3 nm, such as 1 nm to 3 nm, such as 0,5 nm to 2 nm, such as 1 nm to 2 nm, such as 1.5 nm to 2 nm, such as 1.8 nm.

[0031] The primary reflective coating 22 is formed over at least a portion of the second major surface 16, e,g„ over at least a portion of the basecoat 102, If present. The WO 2012/078227 PCT/US2011/052244 primary reflective coating 22 comprises one or more inorganic or organic dielectrics, metals, or semiconductors selected to reflect one or more portions of the electromagnetic spectrum, such as one or more portions in the range of electromagnetic solar radiation. In one non-limiting embodiment, the primary reflective coating 22 comprises one or more radiation reflective metallic films or layers. Examples of suitable reflective metais include, but are not limited to, metallic platinum, iridium, osmium, palladium, aluminum, gold, copper, silver, or mixtures, alloys, or combinations thereof, in one non-limiting embodiment, the primary reflective coating 22 comprises a metallic silver layer having a thickness in the range of 50 nm to 500 nm, such as 50 nm to 300 nm, such as 50 nm to 400 nm, such as 50 nm to 300 nm, such as 70 nm to 300 nm, such as 80 nm to 200 nm, such as 80 nm to 150 nm, such as 90 nm to 150 nm, such as 90 nm to 140 nm, such as 90 nm to 130 nm, such as 100 nm to 130 nm, such as 120 nm to 130 nm. In one particular non-iimiting embodiment, the primary reflective coating 22 comprises metallic silver and has a thickness of at least 50 nm, such as at least 60 nm, such as at least 70 nm, such as at least 80 nm (for example, in the range of 70 nm to 90 nm). The primary reflective coating 22 can be deposited to a thickness such that the article 1 has any particular desired level of reflectance in the desired range of electromagnetic radiation to be reflected. The primary reflective coating 22 can be deposited to a thickness sufficient that the primary coating 22 is opaque in a desired wavelength range, such as visible light. The primary reflective coating 22 can be particularly useful in reflecting visible and solar infrared energy. In one particular non-iimiting embodiment, the primary reflective coating 22 is deposited by a conventional sputtering process, as described in more detail below. In another non-iimiting embodiment, the primary reflective coating 22 can comprise a "high reflector” comprising a plurality of alternating high and low refractive index materials.

[0032] The protective coating 50 assists in protecting the underlying layers, such as the primary reflective layer 22, from mechanical and chemical attack during manufacture, transit, handling, processing, and/or during the mirror’s service life in the field. The protective coating 50 also helps protect the underlying layers from the ingress of liquid water, water vapor, and other environmental pollutants (be they solid, liquid or gas). The protective coating 50 can be an oxygen barrier coating layer to prevent or reduce the passage of ambient oxygen into the underlying layers during subsequent processing, e.g., such as during heating or bending. The protective coating 50 can be of any desired material or mixture of materials, such as but not limited to one or more inorganic materials, in one exemplary embodiment, the protective coating 50 can include a layer having one or more metal oxide materials, such as but not limited to oxides of aluminum, silicon, or mixtures thereof. For example, the protective coating 50 can be a single coating layer comprising in the range of 0 wt.% to 100 wt.% alumina and/or 100 wt.% to 0 wt.% silica, such as 1 wt,% to 8 WO 2012/078227 PCT/US2011/052244 99 wt.% alumina and 99 wt.% to 1 wt.% silica, such as 5 wt% to 95 wl% alumina and 95 wt.% to 5 wt.% silica, such as 10 wt.% to 90 wt.% alumina and 90 wt.% to 10 wt,% silica, such as 15 wt.% to 90 wt% alumina and 35 wt.% to 10 wt.% silica, such as 50 wt.% to 75 wt.% aiumina and 50 wt.% to 25 wt.% silica, such as 50 wt.% to 70 wt.% alumina and 50 wt.% to 30 wt.% silica, such as 35 wt.% to 100 wt% alumina and 65 wt.% to 0 wt.% silica, e.g., 70 wt.% to 90 wt.% aiumina and 30 wt.% to 10 wt.% silica, e.g., 75 wt.% to 85 wt.% alumina and 25 wt.% to 15 wt.% of silica, e.g., 88 wt.% aiumina and 12 wt.% silica, e.g., 65 wt.% to 75 wt.% alumina and 35 wt.% to 25 wt.% silica, e.g., 70 wt.% aiumina and 30 wt.% silica, e.g., 60 wt.% to less than 75 wt.% alumina and greater than 25 wt.% to 40 wt.% silica, in one particular non-limiting embodiment, the protective coating 50 comprises 40 wt.% to 15 wt.% alumina and 60 wt.% to 85 wt.% silica such as 85 wt.% silica and 15 wt.% alumina. Other materials, such as aluminum, chromium, hafnium, yttrium, nickel, boron, phosphorous, titanium, zirconium, and/or oxides thereof, can also be present, such as to adjust the refractive index of the protective coating 50. in one non-limiting embodiment, the refractive Index of the protective coating 50 can be in the range of 1 to 3, such as 1 to 2, such as 1.4 to 2, such as 1.4 to 1.8.

[0033] In one non-iimsting embodiment, the protective coating 50 comprises a combination of silica and alumina. The protective coating 50 can be sputtered from two cathodes (e.g., one silicon and one aluminum) or from a single cathode containing both silicon and aluminum. This siiicon/aluminum oxide protective coating 50 can be written as SixAii.xOk5+x/2, where x can vary from greater than 0 to less than 1. In one specific nonlimiting embodiment, the protective coating 50 can be a siiicon/aluminum oxide coating (SixAI^Ou*^) having a thickness in the range of 5 nm to 5,000 nm, such as 5 nm to 1,000 nm, such as 10 nm to 100 nm, e.g., 10 nm to 50 nm, such as 10 nm to 40 nm, such as 20 nm to 30 nm, such as 25 nm. Further, the protective coating 50 can be of non-uniform thickness. By "non-uniform thickness” is meant that the thickness of the protective coating 50 can vary over a given unit area, e.g., the protective coating 50 can have high and low spots or areas. In another non-limiting embodiment, the protective coating 50 comprises a siiicon/aluminum oxide coating or mixture of silica and aiumina, such as 85 wt.% silica and 15 wt.% alumina, and has a thickness in the range of 10 nm to 500 nm, such as 20 nm to 300 nm, such as 50 nm to 300 nm, e.g., 50 nm to 200 nm, such as 50 nm to 150 nm, such as 50 nm to 120 nm, such as 75 nm to 120 nm such as 75 nm to 100 nm. in a particular non-limiting embodiment, the protective coating 50 can have a thickness of at least 50 nm, such as at least 75 nm, such as at least 100 nm, such as at least 110 nm, such as at least 120 nm, such as at least 150 nm, such as at least 200 nm.

[0034] in another non-limiting embodiment, the protective coating 50 comprises silica having a thickness in the range of 10 nm to 100 nm, such as 10 nm to 80 nm, such as 20 nm 9 WO 2012/078227 PCT/US2011/052244 to 80 nm, such as 30 rsm to 70 nm, such as 40 nm to 60 nm, such as 50 nm. in a further non-limiting embodiment, the protective coating 50 comprises silica having a thickness in the range of 10 nm to 500 nm, such as 10 nm to 400 nm, such as 20 nm to 300 nm, such as 50 nm to 200 nm, such as 75 nm to 150 nm, such as 75 nm to 120 nm.

[0035] In another non-limiting embodiment, the protective coating 50 can comprise a muiti-iayer structure, e.g., a first layer with at least one second layer formed over the first layer. In one specific non-limiting embodiment, the first layer can comprise aiumina or a mixture or alloy comprising aiumina and silica. For example, the first layer can comprise a siiica/alumina mixture having greater than 5 wt.% alumina, such as greater than 10 wt.% aiumina, such as greater than 15 wt.% aiumina, such as greater than 30 wt.% alumina, such as greater than 40 wt,% alumina, such as 50 wt.% to 70 wt.% aiumina, such as in the range of 70 wt.% to 100 wt.% alumina and 30 wt.% to 0 wt.% silica, such as greater than 90 wt.% alumina, such as greater than 95 wt.% aiumina. In one non-limiting embodiment, the first layer comprises all or substantially all aiumina. In one non-limiting embodiment, the first layer can have a thickness in the range of greater than 0 nm to 1 micron, such as 5 nm to 10 nm, such as 10 nm to 25 rsm, such as 10 nm to 15 nm. The second layer can comprise silica or a mixture or alloy comprising silica and alumina. For example, the second layer can comprise a siiica/alumina mixture having greater than 40 wt.% silica, such as greater than 50 wt.% silica, such as greater than 60 wt% silica, such as greater than 70 wt.% silica, such as greater than 80 wt.% silica, such as in the range of 80 wt.% to 90 wt.% silica and 10 wt.% to 20 wt.% alumina, e.g., 85 wt.% silica and 15 wt.% alumina. In one non-limiting embodiment, the second layer can have a thickness in the range of greater than 0 nm to 2 microns, such as 5 nm to 500 nm, such as 5 nm to 200 nm, such as 10 nm to 100 nm, such as 30 nm to 50 nm, such as 35 nm to 40 nm. In another non-limiting embodiment, the second layer can have a thickness in the range of greater than 0 nm to 1 micron, such as 5 nm to 10 nm, such as 10 nm to 25 nm, such as 10 nm to 15 nm. In another non-iimiting embodiment, the protective coating 50 can be a bilayer formed by one metal oxide-containing layer (e.g,, a silica and/or alumina-containing first layer) formed over another metal oxide-containing layer (e.g., a silica and/or alumina-containing second layer). The individual layers of the multilayer protective coating can be of any desired thickness. Non-limiting examples of suitable protective coatings are described, for example, In U.S. Patent Application Nos. 10/007,382; 10/133,805; 10/397,001; 10/422,094; 10/422,095; and 10/422,096.

[0036] As discussed above, the reflective article of the invention can include one or more additional optional films, layers, coatings or structures. Additional reflective articles of the invention incorporating such additional structures will now be described. However, it is to be understood that the specific optional structures or coatings described are not limited to 10 WO 2012/078227 PCT/US20 Π/052244 the pariicuiar illustrated embodiments but that these structures could be utilized interchangeably in any of the embodiments of the invention.

[0037] Another non-limiting reflective article incorporating features of the invention is illustrated in Fig. 1B as a solar mirror 3. In the embodiment illustrated In Fig. 1B, the solar mirror 3 includes a pty 12 with a first major surface 14, Le. an outer major surface, and an opposed second major surface 16, j.e. an inner major surface, as described above. An optional basecoat 102 can be provided over at least a portion of one of the major surfaces, such as the second major surface 16. A primary reflective coating 22 is formed over at least a portion of the second major surface 16, e.g. over at least a portion of the basecoat 102, if present. One or more optional corrosion resistant or anti-corrosion coatings 104 can be provided, e.g,, over at least a portion of the primary reflective coating 22. A primer film 106 can be provided over or under at least a portion of the anti-corrosion coating 104. A topcoat 40 can be provided over at least a portion of the anti-corrosion coating 104, e.g., over at least a portion of the primer film 106. A protective coating 50 can be provided over at least a portion of the topcoat 40. An optional encapsulation structure 24 can be provided over at least a portion of the protective coating 50. While only one anti-corrosion coating 104 is shown, the article could have multiple anti-corrosion coatings 104 and multiple primer films 106 either above and/or below the anti-corrosion coatings 104.

[0038] The ply 12, basecoat 102, primary reflective coating 22, and protective coating 50 can be as described above. However, in this embodiment, the reflective article 3 also comprises other layers having other functions.

[0039] For example, the anti-corrosion coating 104 can provide various benefits, such as corrosion inhibition and ultraviolet screening benefits. Also, the anti-corrosion coating 104 can provide some amount of electromagnetic energy reflection, which can permit a thinner primary reflective layer 22 to be used. The anti-corrosion coating 104 can also provide mechanical and/or chemical protection to the underiying coating layers. The anti-corrosion coating 104 can be provided under, over, or between one or more coating layers, e.g., the primary reflective coating(s) 22 or the top coat 40 (described below). Alternatively or in addition thereto, the anti-corrosion coating 104 can be provided under, over, or between one or more layers of a protective coating 50. It is believed that the anticorrosion coating 104 increases the corrosion resistance of the underiying coatings, and/or enhances the visible light reflective of the solar mirror 3, and/or will block or reduce the passage of UV radiation. Examples of suitable materials for the anti-corrosion coating 104 include, but are not limited to, elemental metals and alloys of two or more metallic elements which are members of Groups 2-16 of the Periodic Table of the Elements, including, but not limited to, nickel and nickel-containing alloys, ferrous alloys and iron-containing alloys such as stainless steels, aluminum and aluminum-containing alloys, copper and copper- 11 WO 2012/078227 PCT/US2011/052244 containing alloys, chromium and chromium-containing alloys, titanium and titanium-containing ailoys, brasses such as Naval brass (an alloy of Cu, Zn and $n), Admiralty brass (an ailoy of Zn, Sn and Cu), and Aluminum brass (an aiioy of Cu, Zn and AI), cobalt and cobait-containing alloys such as ailoys of cobalt and chromium, zinc and zinc-containing alloys, tin and tin-containing alloys, zirconium and zirconium-containing ailoys, molybedenum and molybdenum-containing alioys, tungsten and tungsten-containing alloys, niobium and niobium-containing alloys, indium and indium-containing alloys, lead and lead-containing alloys, and bismuth and bismuth-containing alloys. Specific non-limiting embodiments include corrosion-resistant metals and metal alloys including, but not limited to, nickel and nickel-containing ailoys such as Nickel 200, Inconel(r) alloys such as inconel 600 and Inconel 625, stainless steels such as stainless steel 304 and stainless steel 316, Monel(r) alloys such as Monet 400, Haste!loy(r) alloys, cobalt and cobalt-containing alloys such as Stellite(r) alloys, Inco alloys such as I neo Alloy C-276 and Inco Alloy 020, Incoloy(r) alloys such as Incoloy 300 and Incoloy 325, copper and copper-containing alloys such as brasses especially Naval Brass (approximately 59% copper, 40% zinc, and 1% tin) and Admiralty Brass (approximately 69% copper, 30% zinc, 1 % tin), silicon and silicon-containing alloys, titanium and titanium-containing alloys, and aluminum and aluminum-containing ailoys such as aluminum 6061. if present, the anti-corrosion coating(s) 104 can have any desired thickness. In some non-limiting embodiments, the anti-corrosion coatings 104 can have thicknesses in the range of, but not limited to, 1 nm to 500 nm, such as 1 nm to 400 nm, such as 1 nm to 300 nm, such as 1 nm to 200 nm, such as 1 nm to 100 nm, such as 10 nm to 100 nm, such as 20 nm to 100 nm, such as 30 nm to 100 nm, such as 40 nm to 100 nm, such as 50 nm to 100 nm, such as 20 nm to 40 nm, such as 30 nm to 40 nm, such as 30 nm to 35 nm. in other non-limiting embodiments, the anti-corrosion coating(s) 104 can have a thickness of at least 10 nm, such as at least 20 nm, such as at least 30 nm, such as at least 40 nm, such as at least 50 nm, such as at least 100 nm, such as at least 200 nm. In one particular non-limiting embodiment, the anti-corrosion coating(s) 104 comprise inconel and can have a thickness in the range of 10 nm to 100 nm, such as 10 nm to 80 nm, such as 15 nm to 50 nm, such as 20 nm to 40 nm, such as 30 nm to 40 nm, such as 30 nm to 35 nm. [0040] The optional primer layer 106 can be formed above and/or below the anticorrosion coating(s) 104. The primer layer 106 is serves one or both of the following functions: (a) a chemical getter for oxygen or other chemical species (either endogenous or exogenous to the article) such that they react with the primer layer(s) rather than the primary reflective coating 22, and/or (b) a physical diffusion barrier to prevent chemical species from reaching and affecting (not necessarily by chemical reaction) the primary reflective coating 22, In one specific embodiment, the optional primer layer(s) 106 can comprise a metal or metal alloy which has a strong affinity for oxygen and/or the chemical reaction 12 WO 2012/078227 PCT/US2011/052244 product of the metai or metal alloy with oxygen. The optional primer layer(s) 106 may also comprise materials which constitute a diffusion barrier so as to prevent the diffusion of molecular or atomic oxygen, water vapor, or other gaseous species from chemically reacting with the primary reflective coating 22. In one particular embodiment, the primer layer 106 comprises titanium, titanium oxide, or a mixture/combinatlon thereof. In one particular embodiment, the primer layer 106 can have a thickness in the range of 0.1 to 10 nm, such as 0.5 to 5 nm, such as 0.5 to 4 nm, such as 0.5 to 2 nm, such as 1 nm to 2 rtm.

[0041] The top coat 40 is formed over at least a portion of the primary reflective coating 22, e.g., over at least a portion of the anti-corrosion layer 104, e,g„ over at least a portion of the primer layer 106. The top coat 40 can comprise one or more layers, e.g., one or more dielectric layers, such as one or more metal oxides, nitrides, oxynitrides, borides, fluorides, or carbides. In one non-limiting embodiment, the topcoat 40 can be a single layer comprising a zinc and tin oxide, such as zinc stannate. In another particular non-limiting embodiment, the top coat 40 can comprise a multi-film structure, as described below with respect to Fig. 1C. However, it is to be understood that the invention is not limited to oxide coatings. In one non-limiting embodiment, the topcoat 40 comprises zinc stannate. The top coat can have a thickness of at least 10 nm, such as at least 20 nm, such as at least 50 nm, such as at least 75 nm, such as at least 100 nm, such as at least 150 nm, such as at least 200 nm. In one particular non-limiting embodiment, the top coat can have a thickness in the range of 5 nm to 500 nm, such as 10 nm to 500 nm, such as 50 nm to 500 nm, e.g., 50 nm to 300 nm, such as 100 nm to 250 nm, such as 100 nm to 200 rtm, such as 120 nm to 165 nm, such as 110 nm to 165 nm, such as 120 nm to 140 nm. Generally, the thicker the top coat, the more protection it provided to the underlying coating layers, [0042] The optional encapsulation structure 24 can be formed over and/or around at least a portion of the coated ply 12 described above. In one non-limiting embodiment, the encapsulation structure 24 is formed at least partly by an encapsulating material 92.

Suitable encapsulating materials 92 can include polymeric materials, inorganic materials, or composites, combinations, blends, mixtures, and alloys thereof. When a substantial portion or all of the encapsulation material 92 comprises a polymeric material, the encapsulation material 92 may be deposited by any conventional means, such as but not limited to, brush coating, roll coating, spray coating, curtain coating, dip coating, spin coating, knife-edge coating, screen printing, flood coating, electrocoating (a.k.a, electrodeposition), and powder coating. Suitable polymeric encapsulating materials 92 Include, but are not limited to, thermoplastics, thermosets, elastomers, and thermoplastic elastomers formed by addition polymerization or condensation polymerization, with or without cross-linking, and copolymers, composites, combinations, mixtures, blends, and alloys thereof. However, encapsulants comprising polymeric materials may employ various additives and fillers 13 WO 2012/078227 PCT/US2011/052244 including initiators, photoinitiators, plasticizers, stabilizers, preservatives, biocides, flattening agents, flow agents, antioxidants, UV absorbers, surfactants, dyes, pigments, and inorganic or organic fillers. Potential aif-polymeric encapsulation materials may comprise, but are not limited to, polyacrylates, polyalkyds, polyacrylnitrtles, polyesters, polyfluorocarbons, polyvinyls, polyureas, polyme la mines, and polycarbonates. For example, the encapsulation structure 24 can include acrytic-based coatings, urethane-based coatings, fiuropolymer and/or chlorofluoropolymer coatings (e.g. polyfluroethylene, polychiorotrifluoroethylene, etc), poiyvinyiidene chloride-based coatings, ethylene vinyl alcohol-based coatings, polya cry ionitrile-based coatings, cyclic olefin polymers or copolymer-based coatings, inorgartic/organic composite coatings: organic polymer matrix with one or more inorganic phases (e.g. ceramics like silicon dioxide and aluminum oxide) dispersed within either uniformly or non-uniformly, plasma-sprayed inorganic coatings: ceramics (e.g. silicon dioxide, aluminum oxide, silicon nitride, titanium boride, titanium carbide, boron nitride, silicon carbide) and metals/metal alloys (aluminum, titanium, nickel-based alloys like Inconel, ferrous alloys like stainless steel), vulcanized butadiene-based coatings (e.g., synthetic rubber with sulfur crosslinking), UV-curab!e polysiioxane coatings, laminates comprising polymer interlayers (e.g. ethylene vinyl acetate or poiyvinyiidene chloride interlayers) and glass back plates. In one non-limiting embodiment, the polymeric material is free of heavy metals, such as lead. For encapsulants comprising all inorganic materials, suitable materials include, but are not limited to, metals, metal alloys, or ceramics and composites or combinations thereof. Examples of suitable processes to deposit such inorganic encapsulants include physical vapor deposition (e.g. sputter deposition, electron beam evaporation, thermal evaporation, cathodic arc deposition, plasma spray deposition, flame spray deposition, pyrolytic spray deposition, ion-assisted deposition), chemical vapor deposition (e.g. thermal CVD, plasma-assisted/piasma-enhanced CVD), sol-gel deposition, other wet-chemical processes (e.g. ceramic enamels), and combinations thereof. Further, the encapsulating structure 24 may comprise both polymeric and inorganic materials in combination.

[0043] Specific coatings suitable for the encapsulation structure 24 include, but are not limited to, the Corahond® family of coatings (such as Corabond® HC7707 coating) commercially available from PPG Industries, inc. of Pittsburgh, Pennsylvania, Ferro GAL-1875 "Etch" ceramic enamel, Cosmichrome® coating (commercially available from Gold Touch, Inc.), Sureguard® mirror backing coating (commercially available from Spraylat Corporation), EcoBrite® ink coatings (commercially available from PPG Industries, Inc), PRC 4429 and PRC 4400 coatings commercially available from PRC DeSoto, and Spraytat Lacryl Series 700 or 800 coatings (available from Spraylat Corporation). Alternatively, the encapsulating structure 24 could be metallic, such as formed by one or more metallic layers, 14 WO 2012/078227 PCT/US2011/052244 such as those described above with respect to the anti-corrosion coating 104, formed over the second reflective coating 22 with an optional polymeric material formed over the metallic layer(s). Additional examples of non-polymeric/inorganic encapsulants include ceramic enamels, sehgei ceramic coatings, fiame-sprayed ceramic or metallic coatings, plasma-sprayed ceramic or metallic coatings, and cathodic arc-sprayed ceramic or metallic coatings, in one specific non-limiting embodiment, the encapsulation structure 24 can be a multi-layer structure, such as a bilayer coating having a low lead-containing or fead free basecoat and a low lead-containing or lead free topcoat, [0044j A further non-h'miting solar mirror 10 incorporating features of the invention is illustrated in Fig. 1C. In the embodiment illustrated in Fig. 1C, the soiar mirror 10 includes a first piy 12 with a first major surface 14, i.e, an outer major surface, and an opposed second major surface 16, i.e. an Inner major surface, as described above, in one non-limiting embodiment, an optional secondary reflective coating 20 is formed over at least a portion of the inner surface 16. In another non-limiting embodiment, the optional secondary reflective coating 20 can be formed over at least a portion of the outer major surface 14. A primary reflective coating 22 is formed over at least a portion of the second major surface 16, e.g. over at least a portion of the secondary reflective coating 20 if the secondary reflective coating 20 is present and on the second major surface 16. An anti-corrosion coating 104 can be formed over at least a portion of the primary reflective coating 22. A top coat 40 can be formed over at least a portion of the anti-corrosion coating 104. A protective coating 50 can be formed over at least a portion of the top coat 40. The mirror 10 can also include an encapsulating structure 24.

[0045] The optional secondary reflective coating 20, if present, can provide one or more functions in the solar mirror 10. In one non-limiting embodiment, the secondary reflective coating 20 can be selected to enhance the overall electromagnetic radiation reflection of the reflective article in a particular area or range of electromagnetic radiation. The secondary reflective coating 20 can be selected or designed to enhance the reflection of electromagnetic radiation in one or more portions of the electromagnetic spectrum (e.g, visible, infrared, ultraviolet). In one non-limiting embodiment, the secondary reflective coating 20 can be selected to enhance the reflection of short wavelength radiation, such as less than 600 nm, such as less than 550rim, such as in the range of 400 nm to 550 nm. Alternatively, the secondary reflective coating 20 can be tuned, such as by varying its thickness, to reflect UV radiation. The secondary reflective coating 20 can comprise one or more layers of reflective material, such as one or more layers of meta! oxide materials. In one specific non-iimiting embodiment, the secondary reflective coating 20 comprises alternating layers of a relatively high refractive index material and a relatively iow refractive index material. A “high” refractive index material is any material having an index of refraction 15 WO 2012/078227 PCT/US2011/052244 higher than that of the “low'* refractive index material in one non-limiting embodiment, a low refractive index material is a material having an index of refraction of less than or equal to 1.75. Non-limiting examples of iow refractive index materials include silica, alumina, fluorides (such as magnesium fluoride and caicium fluoride) and alloys, mixtures or combinations thereof. In one non-limiting embodiment, a high refractive index material has an index of refraction greater than 1.75. Non-limiting examples of such materials include titania, zirconia, zinc stannate, silicon nitride, zinc oxide, tin doped zinc oxide, niobium oxide, tantalum oxide, and alloys, mixtures and combinations thereof. The secondary reflective coating 20 can be, for example but not limiting to the present invention, a multilayer coating as shown in Fig. 1C having a first layer 26, e.g., a first dielectric layer, and a second layer 28, e.g., a second dielectric layer. In one non-limiting embodiment, the first layer 26 has a high refractive index and the second layer 28 has a low refractive index. In one non-limiting embodiment, the first layer 26 comprises titania and the second layer 28 comprises silica. In one specific non-limiting embodiment, the first layer, e.g., titania, has a thickness in the range of 15 nm to 35 nm, such 20 nm to 30 nm, such as 22 nm to 27 nm, such as 25 nm. The second layer, e.g., silica, can have a thickness in the range of 30 nm to 60 nm, such 35 nm to 50 nm, such as 40 nm to 50 nm, such as 42 nm. It is to be understood that the materials of the secondary reflective coating 20 are not limited to meta! oxides. Any materials, such as but not limited to oxides, nitrides, oxynitrides, fluorides, etc. could be utilized.

[0046] In the non-limiting embodiment shown in Fig 1C, an optional adhesive layer 30 can be provided between the secondary reflective coating 20 and the primary reflective coating 22. The adhesive layer 30 can be any layer that enhances the adhesion between the secondary and primary reflective coatings 20,22 or improves the mechanical and/or chemical durability of the secondary or primary reflective coatings 20, 22. The adhesive layer 30 can comprise at least one material selected from dielectrics, semiconductors, polymers, organics, or layers of metal or metal alloys. In one non-limiting embodiment, the adhesive layer 30 comprises at least one material selected from oxides, nitrides, or oxynitrides of zinc, tin, titanium, or combinations thereof, such as but not limited to zinc oxide, titania, or a zinc/tin oxide such as zinc stannate. For example, the adhesive layer 30 can have a thickness of less than or equal to 5 nm, such as less than or equal to 4 nm, such as less than or equal to 3 nm, such as less than or equal to 2 nm, such as less than or equal to 1 nm.

[0047] In the illustrated exemplary embodiment shown in Fig. 1C, the top coat 40 is formed over at least a portion of the primary reflective coating 22. The top coat 40 can be as described above, in one specific non-limiting embodiment, the topcoat can comprise one or more layers, e.g., one or more dielectric layers, such as one or more metal oxides, nitrides, 16 WO 2012/078227 PCT/US2011/052244 oxynitrides» borides, fluorides, or carbides. In one particular non-limiting embodiment, the top coat 40 comprises a multi-film structure having a first film 42, e.g., a metal oxide film, a second film 44, e.g., a metal alloy oxide or oxide mixture film, and optionally a third film 46, e.g., a metal oxide film. However, it is to be understood that the invention is not limited to oxide coatings and that other coatings, such as but not limited to nitrides or oxynitrides, could be used, in one non-limiting embodiment, the topcoat 40 can comprise zinc oxide or a zinc/tin oxide, such as zinc stannate, and can have a thickness in the range of 1 nm to 500 nm, such as 5 nm to 500 nm, such as 10 nm to 500 nm, such as 50 nm to 500 nm, e.g., 50 nm to 300 nm, such as 100 nm to 250 nm, such as 100 nm to 200 nm, such as 120 nm to 165 nm.

[0048] In one non-limiting embodiment, the first film 42 can be a zinc-containing film, such as zinc oxide. The zinc oxide film can be deposited from a zinc cathode that includes other materials to improve the conductivity and sputtering characteristics of the cathode. For example, the zinc cathode can include a small amount (e.g., 10 wt.% or less, such as 0 wt% to 5 wt.%) of a conductive material, such as tin, to improve the sputtering characteristics of the cathode. In which case, the resultant zinc oxide film would include a small percentage of tin oxide, e.g., 0 to 10 wt% tin oxide, e.g., 0 to 5 wt.% tin oxide. A coating layer deposited from a zinc cathode having 10 wt.% or less tin is referred to herein as "a zinc oxide” layer even though a small amount of the tin (e.g. 10 wt.%) may be present. The small amount of tin in the cathode is believed to form a smaii amount of tin oxide in the predominantly zinc oxide-containing film. In one non-iimiting embodiment, the zinc oxide first film 42 comprises 90 wt. % zinc and 10 wt.% tin and has a thickness in the range of 1 nm to 200 nm, such as 1 nm to 150 nm, such as 1 nm to 100 nm, such as 1 nm io 50 nm, such as 1 nm to 25 nm, such as 1 nm to 20 nm, such as 1 nm to 10 nm, such as 2‘nm to 8 nm, such as 3 nm to 8 nm, such as 4 nm to 7 nm, such as 5 nm to 7 nm, such as 6 nm.

[0049] In one non-iimiting embodiment, the second film 44 can be a zinc/tin aiioy oxide or zinc/tin oxide mixture film. The zinc/tin alloy oxide can be that obtained from magnetron sputtering vacuum deposition from a cathode of zinc and tin that can comprise zinc and tin in proportions of 10 wt.% to 90 wt.% zinc and 90 wt.% to 10 wt.% tin. One suitable metal alloy oxide that can be present in the second film 44 is zinc stannate. By "zinc stannate” is meant a composition of ZnxSn-|.xO2.x (Formula 1} where “x" varies in the range of greater than 0 to less than 1. For instance, "x” can be greater than 0 and can be any fraction or decimal between greater than 0 to iess than 1. For example where x » 2/3, Formula 1 is Zni^Sn^O^, which is more commonly described as “Zn2SnO4”. A zinc stannate-containing film has one or more of the forms of Formula 1 in a predominant amount in the film. In one non-limiting embodiment, a zinc stannate second film 44 can have a thickness in the range of 1 nm to 200 nm, such as 1 nm to 150 nm, such as 1 nm to 100 nm, 17 WO 2012/078227 PCT/US2011/052244 such as 1 nm to 50 nm, such as 1 nm to 25 nm, such as 1 nm to 20 nm, such as 5 nm to 15 nm, such as 6 nm to 14 nm, such as 8 nm to 14 nm, such as 10 nm to 14 nm, such as 11 nm to 13 nm, such as 12 nm.

[0050] in one non-limiting embodiment, the optional third film 46 can be zinc containing film similar to the first film 42, e.g., a zinc oxide film, in one non-limiting embodiment, the optional zinc oxide third film 46 has a thickness in the range of 1 nm to 200 nm, such as 1 nm to 150 nm, such as 1 nm 100 nm, such as 1 nm to 50 nm, such as 1 nm to 25 nm, such as 1 nm to 10 nm, such as in the range of 2 nm to 8 nm, such as in the range of 3 nm to 8 nm, such as in the range of 4 nm to 7 nm, such as in the range of 5 nm to 7 nm, such as 6 nm.

[0051] In one non-limiting embodiment, the sofar mirror 10 can have a photoactive coating 60, such as a photocatalyfic and/or photohydrophilic coating, formed over at least a portion of the first surface 14. A non-limiting example of one suitable material for the photoactive coating 60 is titania. The photoactive coating 60 can be deposited directly on the first surface 14 or a barrier layer, such as a sodium ion diffusion barrier (SIDB) layer 64 can be provided between the first surface 14 and the photoactive coating 60, A non-limiting example of a suitable SIDB layer material is silica or alumina or combinations thereof, Alternatively, the photoactive coating 60 can be eliminated and just the SiDB layer formed over the first surface 14.

[0052] Some or all of the coatings described above for the reflective articles of the invention can be deposited by any conventional method, such as but not limited to wet chemical methods (e.g. precipitation of the coating from solution, electroless plating, sol-gel chemistry, etc.), electrochemical methods (e.g. eiectroplating/electrodeposition), sputter deposition (e.g, magnetron sputter vapor deposition (MSVD)), evaporation (e.g. thermal or electron beam evaporation), chemical vapor deposition (CVD), spray pyrolysis, flamespraying, or plasma-spraying in one non-iimiting embodiment, some or ail of the coatings can be deposited by MSVD, Examples of MSVD coating devices and methods will be well understood by one of ordinary skill in the art and are described, for example, in U.S. Patent Nos. 4,379,040; 4,861,669; 4,898,789; 4,898,790; 4,900,633; 4,920,006; 4,938,857; 5,328,768; and 5,492,750. For example, the primary reflective coating 22 can be applied by wet chemical methods (e.g. ''wet-silver” deposition -- precipitation of silver from silver nitrate solution), if desired, In one non-limiting embodiment, one or more layers of the secondary reflective coating 20 can be applied by conventional CVD methods, for example on a float glass ribbon while the ribbon is in the tin bath, The primary reflective coating 22 and one or more layers of the top coat 40 can then be applied by a different process, such as MSVD. Alternatively, all of the coatings can be applied by the same process, such as by MSVD. It is believed that applying at least some of the coatings by sputtering has advantages over many 18 WO 2012/078227 PCT/US2011/052244 other techniques. For example, it is possible to deposit a wide range of materials in a single vacuum chamber. Also, sputter deposition is expected to yield layers having higher chemical purity than conventional wet chemistry methods. Further, sputtering eliminates the liquid waste stream produced from wet chemical methods and also enables other metals to be easily deposited. Moreover, sputtering allows inorganic oxides to be deposited to be used for adhesion layers, chemical barriers and mechanical protection.

[0053] The encapsulation structure 24 can be formed over and/or around at least a portion of the coated ply described above. The encapsulation structure 24 is not limited to the examples described above but could include any material to protect the underlying coating materials from chemical and or mechanical attack. For example, in the solar mirror 80 shown In Fig 2, the encapsulation structure 24 includes a second ply 82 connected to the first piy 12, e.g„ to the protective coating 50, by a polymeric layer 84. The second ply 82 can be selected from the materials described above for the first ply 12 and can be the same or different from the first piy 12. Additionally, the second piy 82 need not be transparent to electromagnetic radiation in any portion of the electromagnetic spectrum. [0054] The polymeric layer 84 can be of any desired material and can include one or more layers or plies. The iayer(s) 84 may comprise thermoplastics, thermosets, elastomers, and/or thermoplastic elastomers. The layer 84 can be a polymeric or plastic material such as, for example, polyvinylbutyral, plasticized polyvinyl chloride, or multi-layered thermoplastic materials including polyethyleneterephthalate, ethylene vinyl acetate (EVA), polyvinyl chloride, polyvinylidene chloride, polycarbonate, polyacrylates (e.g. polymethylmethacrylate, polyacrylonitrile), polysiloxanes, fluoropolymers, polyesters, melamines, polyureas, polyurethanes, polyalkyds, polyphenol formaldehydes, etc. Suitable materials are disclosed in, but are not limited to, U.S. Patent Nos, 4,287,107 and 3,762,988, The layer 84 secures the first and second plies together, can provide energy absorption, and can Increase the strength of the laminated structure, in one non-iimitsng embodiment, the layer 84 is polyvinylbutyral and has a thickness in the range of 0.5 mm to 1.5 mm, such as 0.75 mm to 0.8 mm.

[0055] In the solar mirror 90 of the invention shown in Fig. 3, a polymeric encapsulation structure 24 formed at least partly by an encapsulating material 92 as described above can be used. The encapsulating material 92 can wrap around at least part of the sides (minor surfaces) of the solar mirror 90 providing an edge seal for the article. Alternatively, a conventional edge sealant, such as but not limited to polyvinylidene chloride (PVDC), can be applied to the edges, i.e., minor surfaces, of the article before the encapsulating material is applied.

[0056] Another solar mirror 100 of the invention is shown in Fig. 4. The solar mirror 100 includes a first ply 12 as described above, In this embodiment, the secondary 19 WO 2012/078227 PCT/US2011/052244 reflective coating 20 is absent. The primary reflective coating 22 can be applied over at least a portion of the second major surface 16. In one particular embodiment, a basecoat 102 is provided between the second major surface 16 and the primary reflective coating 22, The basecoat 102 can be the same as described above.

[0057] In this embodiment, the primary reflective coating 22 can be any of the materials described above with reference to the earlier embodiments, in one particular embodiment, the primary reflective coating 22 comprises metallic silver having a thickness in the range of 10 nm to 500 nm, such as 50 nm to 500 nm, such 50 nm to 300 nm, such as 50 nm to 200 nm, such as 100 nm to 200 nm, such as 100 nm to 150 nm, such as 110 nm to 140 nm, such as 120 nm to 140 nm, such as 128 nm to 132 nm. In another particular embodiment, the primary reflective coating 22 comprises metallic silver having a thickness in the range of 1 nm to 500 nm, such as 50 nm to 500 nm, such 50 nm to 300 nm, such as 50 nm to 200 nm, such as 50 nm to 150 nm, such as 70 nm to 150 nm, such as 90 nm to 120 nm, such as 90 nm to 130 nm, such as 90 nm to 100 nm, such as 90 nm to 95 nm.

[0058] The top coat 40 can be a single layer or a multi-layer structure having a first layer 110 and a second layer 112. In one particular embodiment, the first metal oxide layer 110 comprises zinc oxide having a thickness in the range of 1 nm to 30 nm, such as 1 nm to 25 nm, such as 5 nm to 20 nm, such as 10 nm to 20 nm, such as 10 nm to 17 nm.

The second layer 112 comprises zinc stannate having a thickness in the range of 10 nm to 100 nm, such as 40 nm to 45 nm.

[0059] The solar mirror 100 can also include a protective coating 114 which can be the same or similar to the protective coating 50 described above, in one particular embodiment, the protective coating 114 comprises silica having a thickness In the range of 10 nm to 500 nm, such as 10 nm to 300 nm, such as 10 nm to 100 nm, such as 20 nm to 100 nm, such as 30 nm to 80 nm, such as 40 nm to 60 nm, such as 50 nm to 60 nm, such as 57 nm.

[0060] Fig. 5 shows a reflective article of the invention (e.g., a solar mirror 1,3,10, 80, 90,100) of the invention mounted on a support base 120. The reflective article Is mounted such that the first major surface 14 faces outwardly. The reflective article can be mounted in any conventional method, such as by an adhesive or by securing the article mechanically in a frame, just to name a few. The base 120 can be connected to the encapsulating structure 24 as described above. Alternatively, the encapsulating structure 24 can be eliminated and the base 120 connected with the outer coating layer of the coating stack, e.g., the protective coating 50. The base 120 can be of any desired material, such as, but not limited to metal (such as aluminum, stainless steel, etc.) or a polymeric material, such as plastic. 20 WO 2012/078227 PCT/US2011/052244 [0061] The invention provides highly reflective articles that are useful in many applications, such as but not limited to solar mirrors. The reflective articles of the invention can have a hemispherical solar-weighted, integrated Rg reflectance (WIRg) of at least 50%, such as at least 60%, such as at feast 70%, such as at least 80%, such as at least 90%, such as at least 91%, such as at least 92%, such as at least 93%, such as at least 94%, such as at least 95%, such as in the range of 90% to 96%.

Corrosion Protection [0062] As discussed above, the reflective articles, particularly in the form of outdoor solar mirrors, can be exposed to harsh environmental conditions. The metallic reflective layer(s) of the solar mirror can corrode or become tarnished when exposed to atmospheric moisture, hydrogen sulfide, atmospheric chloride, and the like. Corrosion or tarnishing of the reflective metallic layer decreases the soiar reflectance of the mirror and reduces the commercial lifetime of the mirror, [0063] In order to address this problem, reflective articles of the invention can include a cathodic protection system to reduce corrosion of the metallic layer.

[0064] Fig. 6 illustrates a passive cathodic protection system 200 attached to a reflective article 202 in the form of a soiar mirror. The reflective article 202 can be of any of the types described above and can include any of the iayer structures described above. For purposes of illustration, the reflective article 202 includes a ply 12 having a primary reflective coating 22 comprising one or more metallic layers, and a protective coating 50. An encapsulation structure 24 is formed on the coated ply 12 and the coated pty 12 and encapsulation structure 24 are optionally attached to a support base 120. Only one primary reflective coating 22 is illustrated In Fig. 6 for ease of discussion. However, it is to be understood that the reflective article 202 could incorporate any number of reflective coatings 22 or any of the other coatings described above with respect to the other embodiments of the reflective articles.

[0065] A contact or conductor 204 is in electrical contact with the metallic fayer(s) of the reflective coating 22. For example, the conductor 204 can extend along a periphery of the coating stack and is in electrical contact with the metallic layers) of the metallic reflective coating 22. The conductor 204 can be, for example, a metal foil or mesh made of a conductive material, such as copper, zinc, magnesium, or the like. The conductor 204 is electrically connected to a sacrificial anode 206 in any conventional manner, such as by a conventional wire 208 or any similar electrically conductive element. In the illustrated embodiment, the anode 206 is shown attached to the support body 120. However, this is simply one configuration of the invention and the anode 206 could be placed anywhere on or near the reflective article 202. 21 WO 2012/078227 PCT/US2011/052244 [0066] The contact/conductor 204 and connector/wire 208 used to make the electrical connection to the sacrificial anode 206 can comprise any electricaliy-conductive material including the case where the same material is used for all three elements (204, 206, and 208). But, in that case, the conductor 204 and connector 208 will also corrode and be sacrificial, Therefore, elements 204 and 208 would also have to be repiaced eventually. For example, one could make the contact/conductor 204 and the sacrificial anode 206 the same element by attaching strips or foils of a sacrificial material to one or more edges ("sidewalls"), or to the rear face, of the mirror. Alternatively, the conductor 204 and connector 208 can be chosen to comprise a material (e.g. gold, platinum, etc.) that is more noble than the material(s) comprising the metallic reflective layer(s) of the reflective coating 22 and more noble than the material comprising the sacrificial anode 206 so that the sacrificial anode 206 will function as intended. Further, there is: (a) an electron conduction path between the sacrificial anode 206 and the materials of the metallic layer(s), and (b) an ton conduction path between the two. The electron conduction path is achieved by ensuring there is electrical continuity between the sacrificial anode 206 and the materials comprising the metallic reflective layer(s), such as via the conductor 204 and connector/conductor 208. The ion conduction path can comprise an electrolytic medium which electrically connects the sacrificial anode 206, connector 208, conductor 204, and metallic reflective layer(s), such as is provided by one or more layers of water vapor molecules which are expected to be typically adsorbed on the surfaces of the aforementioned elements, Of course, a layer of liquid water, such as due to rainwater or condensation of dew, also functions as a suitable electrolytic medium. Alternatively, one could intentionally apply an electrolytic material (e.g. an electrolytic gei or a polymer electrolyte) to the surfaces of the aforementioned elements to ensure that an ion conduction pathway is maintained between the sacrificial anode 206 and the material(s) of the metallic reflective layer(s).

[0067] Electrical contact to the (electricaliy-conductive) reflective iayer(s) of the reflective coating 22 can be made via any electricaliy-conductive material (e.g., electrically conductive thin film coating, conductive paint e.g., “silver paint”, or conductive adhesive, conductive tape or foil, conductive ceramic enamel, etc.) appiied/deposiied on the “sidewall” of the substrate, such that there is electrical continuity between the metallic layer(s) of the reflective coating 22 of the mirror coating and: (a) the sacrificial anode (for "passive" cathodic protection), or alternatively (b) the (DC) negative terminal of a power supply, battery, photovoltaic module, DC-rectified-output of an AC generator (e.g. turbine generator connected to a windmili, etc.) for “active” cathodic, protection described below. There is electrical continuity between the metallic layer(s) and a source of electrons which is at a negative electrical potential relative to the metallic layer(s). These electrons are supplied via the corrosion of a sacrificial anode (passive system) or via a power supply (active system). 22 WO 2012/078227 PCT/US2011/052244

Any method of making electrical contact between such a source of electrons and the metallic layer(s) is suitable. For example, one can make electrical contact to the "face” of the mirror coating, in contrast to the edge/sidewall of the coating, either beiow the encapsulation structure (or via the encapsulation structure, if the encapsulant is electrically conductive) by clamping a conductive electrical clip/lead to the mirror’s coated face. Or, one could apply an electrically conductive paint or conductive adhesive or conductive solder or conductive ceramic enamel to the mirror’s coated face and then attach an electrical lead to that material so as to make electrical contact between the mirror coating’s metallic layer(s) and the sacrificial anode or power supply/source of electrons. Indeed, one could even clamp or solder or glue (using an electricaliy-conductive adhesive/paint) a metal foil (e.g. Zn, Mg, Al, Cu) to the coated surface of the mirror using an electrically-conductive clip or electrically-conductive adhesive/paint such that the foil covers ail or a portion of the mirror coating, indeed, the sacrificial anode couid even comprise a layer of metallic Zn, Mg, Al, or Cu integrated into the mirror coating itself.

[0068] As will be appreciated by one skilled in the art, the anode 206 is a material comprising a metal that is higher in the electromotive series than the metal layer(s) of the primary reflective coating 22. Due to the difference in electrical potential between the cathodically protected metal of the reflective coating 22 and the sacrificial anode 206, the anode 206 has a surplus of electrons and, therefore, corrosion will occur at the anode not the cathode. Such a cathodic protection system will protect the corrodible metal layer(s) of the reflective coating 22 as long as a sufficient amount of sacrificial anode metal remains to supply electrons to the protected structure. When the anode 206 is nearly completely corroded, it can be replaced by another anode 206 to allow the cathodic protection system to continue its function.

[0069] The particular material of the anode 206 can be selected based on the metal used in the metallic layer(s) of the reflective coating 22. For example, if the reflective coating 22 incorporates one or more metallic silver layers, the anode 206 can be formed of material, such as copper, zinc, manganese, etc, having a greater oxidation potential than silver. As would be appreciated by one skilled in the art, should the metallic silver layer of the reflective coating 22 be exposed to potential corrosion inducing materials, the anode 206 will preferentially corrode rather than the silver layer and, thus, enhance the commercial lifetime of the solar mirror. The sacrificial anode 206 should not be in electrical contact with another electrically conductive body. The sacrificial anode 206 should be in electrical contact with the metallic layers) of the mirror coating one wishes to protect from corrosion. For example, if the support base 120 is electrically conductive (e.g., a piece of corrugated steel) the sacrificial anode 206 should be electrically Insulated from the support base 120 23 WO 2012/078227 PCT/US2011/052244 (such as by a non-conductive shield or material) or the anode 206 could be separated from the support base 120.

[0070] An active (impressed current) cathodic protection system can also be incorporated Into or attached to a reflective article of the invention. Figs. 7-9 illustrate an exemplary active cathodic protection system 216 attached to a reflective article 202 as described above. The active cathodic system 216 includes one or more solar panels 218 (or other source of electrons) electrically connected to the metallic reflective layer 22 of the solar mirror 202 and to a suitable anode 206', such as by wires 219 and 221, respectively. The solar panel 218 can be a conventional solar panel formed by an Interconnected assembly of photovoltaic cells or solar cells in the form of a photovoltaic array. The soiar panel generates electricity using light energy through the photovoltaic effect The negative terminals) of the solar panel 218 is connected to the metal layer(s) of the reflective coating 22, such as through one or more contacts or conductors 204'. The positive terminal(s) of the solar panel 218 Is connected to the anode 206'. In this system, a negative electrical bias Is provided to the metallic layer(s) of the reflective coating 22. If oxidizing or corroding agents attack the metal layer(s), the extra electrons provided by the solar panel 218 are consumed rather than oxidation of the metallic layer(s). A regulator can be provided to establish and maintain a desired direct current (DC) voltage level at the output terminals of the solar panel 218. The protection system 216 can also Include an electrical storage device, such as a battery 220. The battery 220 Is connected to the solar panel 218 via a wire 222. The battery 220 is connected to the anode 206’ by a wire 224 and the negative terminal is connected to the metallic layer by a wire 226 and an optional connector 204", A conventional open/closed switch 228 can be connected to the wire 224 and another such switch 230 can be connected to the wire 226. A regulator can be provided to establish and maintain a desired DC voltage level at the output terminals of the battery 220, As will be appreciated by one skilled in the art, the “active” cathodic protection system need not employ solar panels. Any means of supplying electrons (e.g. battery, power supply, etc.) to the material(s) to be protected can be employed. For example, a conventional battery could just be connected to the metal fayer(s) of the reflective coating 22 to supply electrons to prevent corrosion of the metal layer(s). Also, the anode 206' need not be the same as for the passive system described above. In the "active” approach, electrons are supplied to the material(s) to be protected by a power supply, such as a battery, etc,, rather than by corroslon/oxldation of a sacrificial anode. Indeed, the positive terminal of the electron source (solar panel, battery, etc.) can be electrically grounded to the earth such that the anode is simply the earth, [0071] In the illustrated embodiment, under normal operation during daylight hours, a portion of the electricity generated by the solar panel(s) 218 is provided to maintain the 24 WO 2012/078227 PCT/US2011/052244 impressed voltage to the metallic layers). The remainder of the electricity generated by the soiar panel 218 is directed to the battery 220 via the wire 222 for storage. The switches 228 and 230 are open so that the soiar panel 218 provides the impressed current cathodic protection to the metallic iayerfs), while at the same time a portion of the electricity generated by the soiar panel 218 is being stored in the battery 220. During bad weather or at night, the switches 228 and 230 are closed so that the battery 220 provides the impressed voitage to the metallic iayer(s). The switches 228 and 230 can be operated in any conventional manner, such as by timers or by being connected to a central processing unit or similar remote control device.

[0072] It is preferred that the voitage supplied to the metallic Eayer(s) of the reflective coating 22 be sufficient to prevent corrosion of the metal of the metallic layers). For example, the supplied voltage can be regulated to be greater than 5 volts (V), such as at least 6 V, such as at feast 7V, such as at least 8V, such as at (east 9V, such as at least 10V, such as at least 12V, such as at least 15V. For example, the supplied voitage can be in the range of 8V to 15V, such as 10V to 15V.

[0073] Figs. 8 and 9 show one exemplary embodiment of a reflective article 202 with solar panels 218 extending outwardly from a perimeter of the reflective article 202. The soiar panels 218 can be connected to the encapsulation structure 24, to the support base 120, or can be located on the ground adjacent to the solar mirror 202. While the solar panels 218 are shown only on three sides of the article 202, it is to be understood that this is just one exemlpary embodiment and the solar panels 218 could be on one or more sides of the mirror 202, such as on one to four sides of the mirror 202.

[0074] As described above and as shown in the following Examples, an advantage of the reflective article of the invention over conventional wet-chemical mirrors is that the reflective article of the invention can be coated and then heated to a temperature sufficient to heat, treat, or bend the coated article (prior to the application of any polymeric encapsulating structure) without adversely impacting upon the reflectance of the article. Also, coatings of the invention can exhibit an improvement in spectral performance (i.e., an increase in reflectance over some or all of the measured spectral range) and an increase in solar-weighted integrated reflectance after heating. For example, a reflective article of the invention having basecoat and/or primary reflective coating and/or secondary reflective coating and/or anti-corrosion coating and/or topcoat and/or protective coating can be heated to a temperature sufficient to bend or heat treat the article prior to application of the encapsuiation structure. For example, the substrate and coatings could be heated to at least 300°F (149°C), such as at least 350°F (177°C), such as at least 400°F(204°C), such as at least 500°F (260°C), such as at least 750°F (399°C), such as at least 800°F (427°C), such as at least 900°F (482°C), such as at least 1000°F (538°C), such as at least 1022°F (550°C)( 25 WO 2012/078227 PCT/lfS2011/052244 such as at least 1100°F(593°C)f such as at least 1200°F (649^ such as at least 1300°F (704«C), such as in the range of 350°F (177°C) to 1300°F (704°C).

[0075} The invention will now be described with respect to specific examples illustrating various mirror structures incorporating various aspects of the Invention. However, it is to be understood that the invention is not limited to these specific examples.

Examples [0076] Table 1 shows the structure for various mirrors (Samples 1 -10) of the invention. 26 TABLE 1

Sample No. Aq Primer ZiQg ZnO Zn?SnO4 Inconel 600 T Primer ISz ZnO Zn?SnO4 S:85/ AI15 1 1.5 130 2.5 0 12 10 33 0 0 0 0 60 2 1.5 130 2.5 0 9 10 0 0 0 9 0 60 3 1.5 120 1.5 0 12 10 33 0 0 0 0 60 4 1.5 120 1.5 0 9 10 0 0 0 0 0 60 5 1.5 120 1.5 0 0 0 0 0 0 10 21 60 6 1.5 120 0 0 0 0 33 0 0 10 12 60 7 1.5 120 0 0 0 0 33 0 0 0 0 60 δ 1.5 120 1.5 0 5 21 33 0 0 0 0 60 δ 1.8 127 1.6 1.8 0 0 33 0 0 17 42 57 10 1.8 132 0 0 0 0 20 1 0 10 42 57 11 1.6 128 0 0 0 0 33 1 0 0 48 111 12 2 128 0 0 0 0 33 1 0 0 110-120 85-120 13 2 128 0 0 0 0 33 1 0 0 120-165 75-120 14 2 91 0 0 0 0 31 1 0 0 153 100 15 2 95 0 0 0 0 33 1 0 0 137 76 WO 2012/078227 PCT/US2O11/052244 27 WO 2012/078227 PCT/US2011/052244 [0077] Table 2 shows the hemispherical WIRg reflectance (hemispherical solar-weighted, integrated Rg reflectance} of the mirrors of Samples 1-15 before and after heating. From these results, it appears that the hemispherical solar-weighted integrated reflectance of mirrors of the invention can increase upon heating. The “Softening Point" column means that the coated articles were placed in an oven at 1300°F (704°C) and heated (about 5 minutes) to the softening point of the glass (the maximum temperature of the coated surface was approximately 1185°F (641 °C}. TABLE 2

As Deposited 30 mins Softening (unheated) @350°F f177°C) Point

Sample ASTM G-173-3AM-1.5D ISO 9050 ASTM G-173-3AM-1.5D ISO 9050 ASTM G-173-3AM-1.5D ISO 9059 No. 1 92.9 92.7 93.6 93.4 93.1 92.8 2 92.6 92.4 93.5 93.3 94.2 94.1 3 Not Measured Not Measured Not Measured Not Measured Not Measured Not Measured 4 Not Measured Not Measured Not Measured Not Measured Not Measured Not Measured 5 92.8 92.6 93.4 93.3 93.8 93,6 6 92.8 92.6 93.4 93.3 93.9 93,8 7 92.9 92.7 93.5 93.4 93.9 93.7 8 92.9 92.7 93.5 93.3 88.5 88.1 9 92.7 92.4 93.7 93.5 94.2 94,0 10 93.1 92.9 No Data No Data 93.9 93.8 11 94.0 93.8 No Data No Data 95.5 95.3 12 No Data No Data No Data No Data No Data No Data 13 No Data No Data No Data No Data No Data No Data 14 93.7 93.4 No Data No Data 95.4 95,2 15 94.0 93.7 No Data No Data 95.4 95.2 [0078] It will be readily appreciated by those skilled in the art that modifications may be made to the invention without departing from the concepts disclosed in the foregoing description. Accordingly, the particular embodiments described in detail herein are illustrative only and are not limiting to the scope of the invention, which is to be given the full breadth of the appended claims and any and all equivalents thereof. 28