Method for forming a coating

Abstract

A chemical vapor deposition process for forming a manganese oxide-based layer on a glass substrate is provided. A gaseous mixture is formed, the gaseous mixture including one or more manganese-containing compounds selected from the group consisting of bis(cyclopentadienyl)manganese(II), bis(ethylcyclopentadienyl)manganese(II), (methylcyclopentadienyl)manganese(I) tricarbonyl, and derivatives thereof, and one or more oxygen-containing precursors selected from the group consisting of organic oxygen-containing compounds and molecular oxygen. The gaseous mixture is directed toward and along the glass substrate where it reacts to form a manganese oxide coating thereon.

Description

[Technical field]

[0001] The present invention relates generally to a process for forming a manganese oxide-based coating or layer. In particular, the present invention relates to a chemical vapor deposition (CVD) process for forming a manganese oxide-based coating on a glass substrate. Summary of the Invention

[0002] An embodiment of a chemical vapor deposition process for forming a manganese oxide coating is described below. In one embodiment, the chemical vapor deposition process for forming a manganese oxide coating includes providing a moving glass substrate. The gaseous mixture includes a manganese-containing compound and an oxygen-containing molecule. The one or more manganese-containing compounds are selected from the group consisting of bis(cyclopentadienyl)manganese(II), bis(ethylcyclopentadienyl)manganese(II), (methylcyclopentadienyl)manganese(I) tricarbonyl, and derivatives thereof, while the one or more oxygen-containing precursors are selected from the group consisting of organic oxygen-containing compounds and molecular oxygen. The gaseous mixture is directed toward and along the glass substrate. The gaseous mixture reacts on the glass substrate to form a manganese oxide coating on the glass substrate.

[0003] In some embodiments, the glass substrate is a glass ribbon in a float glass manufacturing process.

[0004] In some embodiments, the oxide of manganese coating is formed on the deposition surface of the glass substrate at substantially atmospheric pressure.

[0005] In some embodiments, the method further includes providing a coating apparatus and supplying the gaseous mixture to the coating apparatus prior to forming the oxide of manganese coating on the glass substrate.

[0006] The oxide of manganese coating may be formed on a deposition surface of a glass substrate that is at substantially atmospheric pressure when the gaseous mixture reacts to form the oxide of manganese coating.

[0007] In some embodiments, the oxide of manganese coating forms a continuous coating layer on the glass substrate, while in other embodiments, the oxide of manganese coating forms a discontinuous layer on the glass substrate, with the oxide of manganese covering some areas on the glass substrate and not covering other areas.

[0008] Preferably, the manganese oxide coating has a concentration of 0.10 μg / cm 2 It is deposited to have the following surface manganese concentration:

[0009] There may be embodiments in which the manganese oxide coating is formed over a coating that has been preformed on the glass substrate. Thus, in some embodiments, the manganese oxide coating is formed over a silicon oxide-based coating that has been preformed on the glass substrate. In some embodiments, the manganese oxide coating is formed over a tin oxide-based coating that has been preformed on the glass substrate. The tin oxide-based coating may be undoped or doped, for example with fluorine.

[0010] In some embodiments, the temperature of the glass substrate is between 1100° F. (593° C.) and 1400° F. (760° C.) when the manganese oxide coating is formed thereon, and the manganese oxide coating is pyrolytic.

[0011] In some embodiments, an organic oxygen-containing compound is included in the gaseous mixture, the organic oxygen-containing compound being composed of one or more carbonyl compounds. In a specific embodiment, the organic oxygen-containing compound is an ester, and may further be an ester having an alkyl group with a β-hydrogen. The organic oxygen-containing compound may be one or more of ethyl acetate, ethyl formate, ethyl propionate, isopropyl formate, isopropyl acetate, n-butyl acetate, and t-butyl acetate. In a particularly preferred embodiment, the organic oxygen-containing compound is ethyl acetate.

[0012] In some embodiments, the gaseous mixture is comprised of molecular oxygen.

[0013] In some embodiments, the gaseous mixture is comprised of (methylcyclopentadienyl)manganese(I) tricarbonyl or its derivatives, or both. In a preferred embodiment, the gaseous mixture is comprised of (methylcyclopentadienyl)manganese(I) tricarbonyl.

[0014] In some embodiments, the gaseous mixture is comprised of (methylcyclopentadienyl)manganese(I) tricarbonyl and the organic oxygen-containing compound is comprised of ethyl acetate.

[0015] The above, and other advantages of the present process will become readily apparent to those skilled in the art when considered in light of the following detailed description taken in conjunction with the accompanying drawing, which is a schematic illustration of a vertical cross-section of equipment for carrying out a float glass manufacturing process according to one embodiment of the present invention. [Brief description of the drawings]

[0016] [Figure 1] FIG. 1 is a schematic diagram in vertical section of an installation for carrying out a float glass manufacturing process according to one embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] It is to be understood that the present invention may assume various alternative orientations and step sequences unless expressly specified to the contrary. It is also to be understood that the specific articles, devices, and processes described in the following specification are merely exemplary embodiments of the inventive concepts. Thus, specific dimensions, orientations, or other physical characteristics relating to the disclosed embodiments are not to be considered as limiting, unless expressly stated otherwise. Also, although not necessarily, similar elements in the various embodiments described within this section of the application may be generally referred to by similar reference numerals.

[0018] In the context of the present invention, when a layer or coating is said to be "based" on a particular material or materials, this means that the layer or coating consists primarily of the corresponding material or materials, typically comprising at least about 50 atomic % of the material or materials.

[0019] In the following description of the invention, unless specifically stated to the contrary, the disclosure of alternative values ​​at the upper or lower limits of an acceptable range of a parameter, in combination with an indication that one of the values ​​is preferred over the other, is to be construed as implicitly indicating that each intermediate value of that parameter between the more preferred and less preferred of the alternative values ​​is itself preferred over the less preferred value, and is preferred over each intermediate value between the less preferred value and the intermediate value.

[0020] Throughout this specification, the terms "comprise" or "comprising" mean including the specified components but do not exclude the presence of other components. The terms "consisting essentially of" or "consisting essentially of" mean including the specified components but excluding materials present as impurities, unavoidable materials present as a result of the process used to provide the components, and components other than components added for purposes other than achieving the technical effect of the invention. Generally, when referring to a composition, a composition that consists essentially of a set of components will contain less than 5% by weight, typically less than 3% by weight, and more typically less than 1% by weight of unspecified components.

[0021] The term "about" as used herein includes the stated value and means within an acceptable range of deviation of a particular value as determined by one of ordinary skill in the art, taking into account the measurement in question and the error associated with the measurement of a particular quantity (i.e., the limitations of the measurement system). For example, "about" can mean within one or more standard deviations, as would be understood by one of ordinary skill in the art. Furthermore, although a parameter may be described herein as having "approximately" a particular value, it should be understood that, according to an embodiment, the parameter may be exactly or approximately a particular value within the range of measurement error, as would be understood by one of ordinary skill in the art.

[0022] The terms "consisting of" or "consisting of" mean the inclusion of the specified elements but the exclusion of other elements.

[0023] Wherever appropriate and depending on the context, use of the words "comprise" or "comprising" may also be interpreted as including the meaning "consisting essentially of" or "consisting essentially of" and also as including the meaning "consisting of" or "consisting of".

[0024] References herein such as "in the range of x to y" are intended to include the interpretation "from x to y" and therefore include values ​​x and y.

[0025] In the context of this invention, a transparent material or substrate is a material or substrate that is capable of transmitting visible light so that objects or images beyond or behind the material can be clearly seen through the material or substrate.

[0026] In the context of the present invention, the "thickness" of a layer is represented, for any given location on the surface of the layer, by the distance through the layer from that location on the surface of the layer to a location on the opposite surface of the layer in the direction of the smallest dimension of the layer.

[0027] In the present invention, a "derivative" is a chemical entity that is structurally related to and theoretically derivable from another chemical entity.

[0028] In one embodiment of the present invention, a CVD process for forming a manganese oxide coating is provided. The CVD process is described in the context of coated glass products. Such coated glass products may be used in a variety of applications. For example, but not limited to, the coated glass products may be utilized in architectural glass, electronics, and / or automotive and aerospace applications. They may be used as an absorber layer in solar control products or as a layer in a multi-coating stack design to mimic a particular colored product.

[0029] The oxide of manganese coating comprises manganese and oxygen. In certain embodiments, the oxide of manganese coating may consist essentially of manganese and oxygen. The oxide of manganese coating may also include trace amounts of one or more additional components, such as, for example, carbon. As used herein, the term "trace amount" refers to the amount of the component in the oxide of manganese based layer being less than 0.01% by weight, or equivalently, less than 100 ppm.

[0030] In certain embodiments, the oxide of manganese coating forms a continuous layer on the glass substrate. However, in other embodiments, the oxide of manganese coating forms a discontinuous layer on the glass substrate, with the oxide of manganese covering some areas on the glass substrate but not other areas on the glass substrate. In certain preferred embodiments, the oxide of manganese coating has a surface concentration of manganese of less than 0.10 μg / cm 2 Less than or equal to 0.07 μg / cm 2 Less than 0.05 μg / cm, more preferably 0.05 μg / cm 2 It can be deposited on a glass substrate as follows:

[0031] The CVD process may be performed in conjunction with the manufacture of the glass substrate. In one embodiment, the glass substrate may be formed utilizing a known float glass manufacturing process. An example of a float glass manufacturing process is shown in the figure. In this embodiment, the glass substrate may also be referred to as a glass ribbon. However, it should be understood that the CVD process may be utilized separately from the float glass manufacturing process or well after the formation and cutting of the glass ribbon.

[0032] In certain embodiments, the CVD process is a dynamic deposition process. In these embodiments, the glass substrate is moving as the manganese oxide coating is formed. Preferably, the glass substrate moves at a predetermined speed, for example, greater than 3.175 m / min (125 in / min) as the manganese oxide coating is formed. In one embodiment, the glass substrate moves at a speed between 3.175 m / min (125 in / min) and 12.7 m / min (600 in / min) as the manganese oxide coating is formed.

[0033] In certain embodiments, the glass substrate is heated. In one embodiment, the temperature of the glass substrate when the manganese oxide coating is formed is greater than or equal to about 1100° F. (593° C.). In another embodiment, the temperature of the glass substrate when the manganese oxide coating is formed thereon is between 1100° F. (593° C.) and 1400° F. (760° C.).

[0034] Preferably, the manganese oxide coating is deposited on the deposition surface of the glass substrate while the deposition surface is at substantially atmospheric pressure. In this embodiment, the CVD process is an atmospheric pressure CVD (APCVD) process. However, the CVD process is not limited to an APCVD process, and in other embodiments, the manganese oxide coating may be formed under low pressure conditions.

[0035] The glass substrate is not limited to a particular thickness. Also, the glass substrate can be of any conventional glass composition known in the art. In one embodiment, the glass substrate is soda-lime-silica glass. In some embodiments, the substrate can be part of a float glass ribbon. However, the CVD process is not limited to soda-lime-silica glass substrates, and in other embodiments, the glass substrate can be, for example, borosilicate glass or aluminosilicate glass.

[0036] Also, the transparency or absorption properties of the glass substrate may vary between embodiments. Additionally, the color of the glass substrate may vary between embodiments of the CVD process. In one embodiment, the glass substrate may be substantially transparent. In other embodiments, the glass substrate may be tinted or colored.

[0037] Manganese oxide coatings may be deposited by providing one or more manganese-containing compounds selected from the group consisting of bis(cyclopentadienyl)manganese(II), bis(ethylcyclopentadienyl)manganese(II), (methylcyclopentadienyl)manganese(I) tricarbonyl, and derivatives thereof, and one or more oxygen-containing precursors selected from the group consisting of organic oxygen-containing compounds and molecular oxygen.

[0038] A separate supply line may extend from a source of reactant (precursor) molecules. As used herein, the phrases "reactant molecules" and "precursor molecules" are used interchangeably to refer to any or all of the manganese-containing compounds and oxygen-containing precursors and / or to describe the various embodiments thereof disclosed herein. Preferably, the source of precursor molecules is provided at a location outside the float bath chamber.

[0039] Preferably, the oxide of manganese coating is deposited by forming a gaseous mixture. The precursor molecules used to form the gaseous mixture are preferably suitable for use in a CVD process. Such molecules may be liquid or solid at one point, but may be volatile and therefore vaporized for use in the gaseous mixture. In certain embodiments, the gaseous mixture includes precursor molecules suitable for forming an oxide of manganese coating at substantially atmospheric pressure. Once in a gaseous state, the precursor molecules may be included in a gas stream and utilized to form the oxide of manganese coating.

[0040] In some embodiments, the gaseous mixture formed to deposit the manganese oxide coating is comprised of an organic oxygen-containing compound. The organic oxygen-containing compound can be one or more carbonyl compounds. Preferably, the carbonyl compound is an ester. More preferably, the carbonyl compound is an ester having an alkyl group with a β hydrogen. An alkyl group with a β hydrogen containing 2 to 10 carbon atoms is preferred. Preferably, the ester is selected from one or more of ethyl acetate (EtOAc), ethyl formate, ethyl propionate, isopropyl formate, isopropyl acetate, n-butyl acetate, and t-butyl acetate. Most preferably, the oxygen-containing compound is ethyl acetate.

[0041] In other embodiments of the invention, the gaseous mixture includes molecular oxygen, or molecular oxygen in addition to an organic oxygen-containing compound.

[0042] In one embodiment, the manganese-containing compound is comprised of (methylcyclopentadienyl)manganese(I) tricarbonyl or its derivatives or both. In a preferred embodiment, the manganese-containing compound is comprised of (methylcyclopentadienyl)manganese(I) tricarbonyl and the oxygen-containing precursor is comprised of ethyl acetate. In another embodiment, the gaseous mixture is comprised of molecular oxygen and (methylcyclopentadienyl)manganese(I) tricarbonyl.

[0043] The gaseous mixture may also include one or more inert gases utilized as carrier or diluent gases. Suitable inert gases include nitrogen (N2), helium (He), and mixtures thereof. Thus, one or more sources of inert gas may be provided to which separate supply lines may extend.

[0044] The precursor molecules are mixed to form a gaseous mixture. In certain embodiments, a coating apparatus may be provided. Preferably, the gaseous mixture is fed to the coating apparatus prior to forming the manganese oxide coating on the glass substrate. The gaseous mixture may be exhausted from the coating apparatus utilizing one or more gas distribution beams. Preferably, the gaseous mixture is formed prior to being fed to the coating apparatus. For example, the precursor molecules may be mixed in a feed line connected to an inlet of the coating apparatus. In other embodiments, the gaseous mixture may be formed within the coating apparatus.

[0045] Preferably, the coating device extends over the entire glass substrate and is provided at a predetermined distance above the glass substrate. The coating device is located at at least one predetermined position. When utilizing a CVD process in combination with a float glass manufacturing process, the coating device is preferably provided in the float bath section. However, the coating device may be provided in the annealing furnace and in the gap between the float bath and / or the annealing furnace.

[0046] The gaseous mixture is directed toward and along the glass substrate. Using the coating apparatus, the gaseous mixture is directed toward and along the glass substrate. Preferably, the gaseous mixture is directed toward and along the glass substrate in a laminar flow.

[0047] The gaseous mixture reacts at or near the glass substrate to form a manganese oxide coating thereon. In some embodiments, the manganese oxide coating is pyrolytic. As used herein, the term "pyrolytic" may refer to a coating that is chemically bonded to the glass substrate.

[0048] The manganese oxide coating of the present invention may be formed on one or more previously deposited coatings. For example, the manganese oxide coating may be formed on a pre-deposited silicon oxide coating formed on the deposition surface of the glass substrate. The manganese oxide coating may be formed directly on the silicon oxide coating. In other embodiments, the manganese oxide coating may be formed on a pre-deposited tin oxide coating formed on the deposition surface of the glass substrate. In these embodiments, the tin oxide coating may be undoped or doped, and if the tin oxide coating is doped, it may be doped with fluorine. The manganese oxide coating may be formed directly on the tin oxide coating.

[0049] As explained above, the oxide of manganese coating may be formed contemporaneously with the manufacture of the glass substrate in a known float glass manufacturing process, which is typically carried out utilizing a float glass facility, such as the facility 30 shown in the figures. However, it should be understood that the float glass facility 30 described herein is merely exemplary of such a facility.

[0050] As shown, the float glass facility 30 may include a canal section 32 along which molten glass 34 is transported from a melting furnace to a float bath section 36 where the glass substrate is formed. In this embodiment, the glass substrate is referred to as a glass ribbon 38. The glass ribbon 38 is the preferred substrate upon which the manganese oxide coating is formed. However, it should be understood that the glass substrate is not limited to a glass ribbon.

[0051] In an embodiment of the invention, the glass ribbon 38 advances from the bath section 36 through an adjacent annealing furnace 40 and a cooling section 42. The float bath section 36 includes a bottom section 44 containing a bath of molten tin 46, a roof 48, an opposing sidewall (not shown), and end walls 50, 52. The roof 48, the sidewalls and the end walls 50, 52 together define an enclosure 54 within which a non-oxidizing atmosphere is maintained to prevent oxidation of the molten tin 46.

[0052] During operation, the molten glass 34 flows along the canal 32 under the regulating tweezers 56 and flows downwards in a controlled amount towards the surface of the tin bath 46. At the surface of the molten tin, the molten glass 34 spreads laterally due to the effects of gravity and surface tension, as well as certain mechanical effects, and advances across the tin bath 46 to form a glass ribbon 38. The glass ribbon 38 is removed from the bath section 36 via lift-out rolls 58 and is then transported on aligned rolls through the annealing furnace 40 and cooling section 42. The deposition of the manganese oxide coating is preferably carried out in the float bath section 36, although it may also be possible to carry out the deposition further down the glass production line, for example in the gap 60 between the float bath 36 and the annealing furnace 40, or within the annealing furnace 40.

[0053] As shown, a coating apparatus 62 is provided within the float bath section 36. A manganese oxide coating may be formed utilizing the coating apparatus 62. In this embodiment, the manganese oxide coating may be formed directly on the glass substrate. In certain embodiments, the manganese oxide coating may be formed over one or more coatings previously formed on the glass ribbon 38. Each of these coatings may be formed utilizing a separate coating apparatus. For example, in one embodiment, a coating layer including tin oxide may be deposited utilizing coating apparatuses 62, 64. In this embodiment, the manganese oxide coating may be formed directly or over an undoped tin oxide coating utilizing separate coating apparatuses 64-68 located downstream of the coating apparatuses 62, 64 used to form the tin oxide coating within the float bath section 36 or in another portion of the float glass facility 30. In another embodiment, a coating apparatus 66 may be provided and utilized to form a coating including fluorine-doped tin oxide. In this embodiment, the manganese oxide coating may be formed directly or over a doped tin oxide coating utilizing a coating apparatus 68 located downstream of the coating apparatus 66.

[0054] A suitable non-oxidizing atmosphere, generally nitrogen or a mixture of nitrogen and hydrogen with nitrogen being the predominant component, is maintained in the float bath section 36 to prevent oxidation of the molten tin 46 which constitutes the float bath. Atmospheric gas is introduced through a conduit 70 operably connected to a distribution manifold 72. The non-oxidizing gas is introduced at a rate sufficient to replace normal losses and maintain a slight positive pressure, on the order of about 0.001 to about 0.01 atmospheres above ambient atmospheric pressure, to prevent ingress of outside atmosphere. For purposes of the present description, the above pressure ranges will be considered to constitute normal atmospheric pressure.

[0055] Preferably, the manganese oxide coating is formed at substantially atmospheric pressure. Thus, the pressure in the float bath section 36, the annealing furnace 40, and / or the gap 60 between the float bath section 36 and the annealing furnace 40 may be substantially atmospheric pressure.

[0056] Heat to maintain the desired temperature conditions within the float bath section 36 and the enclosure 54 may be provided by radiant heaters 74 within the enclosure 54. Because the cooling section 42 is not enclosed and the glass ribbon 38 is open to the surrounding atmosphere, the atmosphere within the annealing furnace 40 is typically atmospheric. The glass ribbon 38 is then cooled to ambient temperature. To cool the glass ribbon 38, ambient air may be directed at the glass ribbon 38, such as by a fan 76 in the cooling section 42. A heater (not shown) may also be provided within the annealing furnace 40 to gradually reduce the temperature of the glass ribbon 38 according to predetermined conditions as it passes therethrough. EXAMPLES

[0057] The following examples are presented solely for the purpose of further illustrating and disclosing embodiments of a process for depositing an oxide of manganese coating in accordance with the present invention, and should not be construed as limiting the present invention.

[0058] Example 1 illustrates the deposition of a manganese oxide coating deposited in a lab coater directly onto a pyrolytic silicon oxide coating previously formed on a glass substrate. The glass substrate was soda-lime-silica based and was moving at a line speed of 100 in / min as the manganese oxide coating was deposited. The manganese oxide coating was deposited by forming a gaseous mixture of bis(cyclopentadienyl)manganese(II) and ethyl acetate. The flow rates were 0.90 standard liters per minute ("slpm") for bis(cyclopentadienyl)manganese(II) and 0.94 slpm for ethyl acetate. These precursor molecules were mixed to form a gaseous mixture, which was then fed into a lab coating apparatus and directed toward and along the glass substrate. The estimated gas phase concentrations were 0.50% for bis(cyclopentadienyl)manganese(II) and 1.45% for ethyl acetate, with the remainder being nitrogen. Manganese oxide was uniformly coated onto the glass substrate at a deposition rate of 44 Å / sec. The coating thickness was determined by optical modeling to be 400 Å.

[0059] Examples 2-4 demonstrate the deposition of manganese oxide coatings deposited in a lab coater directly onto pyrolytic tin oxide coatings previously formed on glass substrates. In each of Examples 2-4, the glass substrate was soda-lime-silica based and was moving at a line speed of 200 in / min at the time the manganese oxide coating was deposited. The manganese oxide coatings were deposited by forming a gaseous mixture of bis(cyclopentadienyl)manganese(II) and ethyl acetate. The flow rates of these precursors were as follows: Example 2 0.10 slpm bis(cyclopentadienyl)manganese(II) and 0.12 slpm ethyl acetate, Example 3 0.20 slpm bis(cyclopentadienyl)manganese(II) and 0.23 slpm ethyl acetate, Example 4 0.30 slpm bis(cyclopentadienyl)manganese(II) and 0.35 slpm ethyl acetate. The precursor molecules were mixed to form a gaseous mixture that was then fed into a lab coating apparatus and directed toward and along the glass substrate. The estimated gas phase concentrations were as follows: Example 2 0.06% bis(cyclopentadienyl)manganese(II) and 0.18% ethyl acetate, Example 3 0.12% bis(cyclopentadienyl)manganese(II) and 0.35% ethyl acetate, Example 4 0.18% bis(cyclopentadienyl)manganese(II) and 0.54% ethyl acetate. In each case, the remainder was nitrogen. The manganese oxide coatings of Examples 2-4 were discontinuous coatings, with manganese oxide covering some areas of the glass substrate and not covering other areas. For each of Examples 2-4, the surface concentration of manganese was measured using inductively coupled plasma optical emission spectroscopy (ICP-OES) and was found to be 0.35 μg / cm for Example 2. 2 , and 1.60 μg / cm in Example 3. 2 , and 2.30 μg / cm in Example 4. 2 It was.

[0060] Examples 5-7 demonstrate the deposition of manganese oxide coatings deposited in a lab coater directly onto pyrolytic tin oxide coatings previously formed on glass substrates. In each of Examples 5-7, the glass substrate was soda-lime-silica based and was moving at a line speed of 47 in / min at the time the manganese oxide coating was deposited. The manganese oxide coating was deposited by forming a gaseous mixture of (methylcyclopentadienyl)manganese(I) tricarbonyl and molecular oxygen (O2). The flow rates of these precursors are as follows: Example 5 0.75 slpm (methylcyclopentadienyl) manganese(I) tricarbonyl and 0.50 slpm O2, Example 6 1.00 slpm (methylcyclopentadienyl) manganese(I) tricarbonyl and 0.50 slpm O2, Example 7 0.50 slpm (methylcyclopentadienyl) manganese(I) tricarbonyl and 0.50 slpm O2. The precursor molecules were mixed to form a gaseous mixture that was passed through a lab coating apparatus and then flowed onto and along the glass substrate. The estimated gas phase concentrations are as follows: Example 5: 0.79% (methylcyclopentadienyl) manganese(I) tricarbonyl and 2.10% O2, Example 6: 1.06% (methylcyclopentadienyl) manganese(I) tricarbonyl and 2.10% O2, Example 7: 0.53% (methylcyclopentadienyl) manganese(I) tricarbonyl and 2.10% O2, the remainder being nitrogen. The manganese oxide coatings in Examples 5-7 were discontinuous coatings, with manganese oxide covering parts of the glass substrate and not covering other parts. For each of Examples 5-7, the manganese oxide coverage was measured using X-ray photoelectron spectroscopy (XPS) to be 73.0% in Example 5, 83.6% in Example 6, and 63.5% in Example 7.

[0061] Examples 8-10 illustrate the deposition of manganese oxide coatings where the glass substrate was soda lime silica based, formed in conjunction with a float glass manufacturing process, and was moving at a line speed of 472 in / min as the coating layer was deposited in a heated zone of the float glass manufacturing process. A pyrolytic tin oxide coating was deposited on the glass substrate, and a manganese coating was deposited on the tin oxide coating. The manganese oxide coating was deposited by forming a gaseous mixture of (methylcyclopentadienyl)manganese(I) tricarbonyl and ethyl acetate. The flow rates of these precursors are as follows: Example 8: 3.5 cc / min (methylcyclopentadienyl) manganese(I) tricarbonyl and 17.6 cc / min ethyl acetate, Example 9: 2.5 cc / min (methylcyclopentadienyl) manganese(I) tricarbonyl and 17.6 cc / min ethyl acetate, Example 10: 1.0 cc / min (methylcyclopentadienyl) manganese(I) tricarbonyl and 17.6 cc / min ethyl acetate. The precursor molecules were mixed to form a gaseous mixture that was then fed into the coating apparatus and then directed towards and along the glass ribbon. The estimated gas phase concentrations were as follows: Example 8: 0.11% (methylcyclopentadienyl) manganese(I) tricarbonyl and 0.88% ethyl acetate, Example 9: 0.08% (methylcyclopentadienyl) manganese(I) tricarbonyl and 0.88% ethyl acetate, Example 10: 0.03% (methylcyclopentadienyl) manganese(I) tricarbonyl and 0.88% ethyl acetate, the balance being nitrogen. The manganese oxide coatings of Examples 8-10 were discontinuous coatings, with manganese oxide covering some areas of the glass substrate and not covering other areas. For each of Examples 8-10, the surface concentration of manganese was measured using ICP-OES and found to be 0.58 μg / cm for Example 8. 2 , and 0.25 μg / cm in Example 9. 2 , and 0.10 μg / cm in Example 10. 2 It was.

[0062] The foregoing is considered as merely illustrative of the principles of the invention. Moreover, since numerous modifications and changes will readily occur to those skilled in the art, it is not desired to limit the invention to the exact construction and process shown and described. Accordingly, all suitable modifications and equivalents are deemed to be within the scope of the invention.

Claims

1. 1. A chemical vapor deposition process for forming a manganese oxide coating on a glass substrate, comprising: providing a glass substrate; forming a gaseous mixture comprised of one or more manganese-containing compounds selected from the group consisting of bis(cyclopentadienyl)manganese(II), bis(ethylcyclopentadienyl)manganese(II), (methylcyclopentadienyl)manganese(I) tricarbonyl, and derivatives thereof, and one or more oxygen-containing precursors selected from the group consisting of organic oxygen-containing compounds and molecular oxygen; directing the gaseous mixture towards and along the glass substrate; reacting the gaseous mixture on the glass substrate to form a coating of manganese oxide on the glass substrate; 1. A chemical vapor deposition process for forming a manganese oxide coating on a glass substrate, comprising:

2. 10. The chemical vapor deposition process of claim 1, wherein the glass substrate is a glass ribbon in a float glass manufacturing process.

3. 3. The chemical vapor deposition process of claim 1 or 2, further comprising the steps of providing a coating apparatus and supplying the gaseous mixture to the coating apparatus prior to forming the oxide of manganese coating on the glass substrate.

4. 3. The chemical vapor deposition process of claim 1 or 2, wherein the manganese oxide coating is formed on the deposition surface of the glass substrate, which is at substantially atmospheric pressure when the gaseous mixture reacts to form the manganese oxide coating.

5. 3. The chemical vapor deposition process of claim 1 or 2, wherein the manganese oxide coating forms a continuous coating layer on the glass substrate.

6. 3. The chemical vapor deposition process of claim 1 or 2, wherein the manganese oxide coating forms a discontinuous coating layer on the glass substrate.

7. The manganese oxide coating has a concentration of 0.10 μg / cm ２ 3. The chemical vapor deposition process of claim 1 or 2 having a surface manganese concentration of:

8. 3. The chemical vapor deposition process of claim 1 or 2, wherein the manganese oxide coating is formed on a pre-formed coating on the glass substrate.

9. 3. The chemical vapor deposition process of claim 1 or 2, wherein the manganese oxide coating is formed on a silicon oxide-based coating that has been previously formed on the glass substrate.

10. 3. The chemical vapor deposition process of claim 1 or 2, wherein the manganese oxide coating is formed on a tin oxide-based coating that has been pre-formed on the glass substrate.

11. The chemical vapor deposition process of claim 10 , wherein the tin oxide based coating is doped with fluorine.

12. 3. The chemical vapor deposition process of claim 1 or 2, wherein the glass substrate is at a temperature of 1100°F (593°C) to 1400°F (760°C) when the manganese oxide coating is formed thereon.

13. 3. The chemical vapor deposition process of claim 1 or 2, wherein the manganese oxide coating is pyrolytic.

14. 3. The chemical vapor deposition process of claim 1 or 2, wherein an organic oxygen-containing compound is included in the gaseous mixture, the organic oxygen-containing compound consisting of one or more carbonyl compounds.

15. 15. The chemical vapor deposition process of claim 14, wherein the organic oxygen-containing compound is an ester.

16. 16. The chemical vapor deposition process of claim 15, wherein the organic oxygen-containing compound is an ester having an alkyl group with a β hydrogen.

17. 15. The chemical vapor deposition process of claim 14, wherein the organic oxygen-containing compound is one or more of ethyl acetate, ethyl formate, ethyl propionate, isopropyl formate, isopropyl acetate, n-butyl acetate, and t-butyl acetate.

18. 15. The chemical vapor deposition process of claim 14, wherein the organic oxygen-containing compound is ethyl acetate.

19. 3. The chemical vapor deposition process of claim 1 or 2, wherein the gaseous mixture consists of molecular oxygen.

20. 3. The chemical vapor deposition process of claim 1 or 2, wherein the gaseous mixture is comprised of (methylcyclopentadienyl)manganese(I) tricarbonyl and / or a derivative thereof.

21. 3. The chemical vapor deposition process of claim 1 or 2, wherein the gaseous mixture consists of (methylcyclopentadienyl)manganese(I) tricarbonyl.

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