A decorative article having visually distinct etched and non-etched portions

Abstract

The present invention proposes the concept of a non-dissolvable, chemically treated coating to achieve visually observable distinct patterns or writings or designs or decorations. Such distinctiveness is provided by modification of the functional coating properties during thermal processing resulting in a new chemistry in some portions of the underlying coating. The other portions may be uncoated, retaining the original properties of the underlying coating. The present application also provides a method for making decorative glass articles having a distinct etched portions and non-etched portions.

Description

[0001] A DECORATIVE ARTICLE HAVING VISUALLY DISTINCT ETCHED AND NON-ETCHED PORTIONS

[0002] TECHNICAL FIELD

[0003] The present disclosure generally relates to a decorative glass article having visually distinct etched and non-etched portions. Specifically, the disclosure relates to a decorative glass article having a textured or patterned appearance arising from a chemical reaction between coatings deposited over portions of the glass substrate and the underlying coating on the surface of the glass substrate. The deposited coatings establish a distinct appearance between portions of the glass substrate coated with it and portions of the glass substrate not coated with it. The invention is also directed to methods of making such decorative glass articles.

[0004] BACKGROUND

[0005] Decorative or patterned coatings on glass substrates are known to have a variety of applications in decorative wall panels, partitions, windows, doors, tables, facades, spandrels etc., in residential or corporate buildings. Decorative patterned glass articles are such articles where a glass substrate is usually deposited or coated or printed or embossed with various appealing patterns or different images, with one or more functional or performance or optical layers. These articles are used not just for their functional purpose, but also provide an aesthetically enhanced appearance to the spaces, by changing the look and feel of the spaces fitted therewith. Such decorative glass articles provide heavenly aesthetics and are highly appealing to customers when provided in different colors and shades.

[0006] It is known that certain coatings or combinations of coatings alter the interaction between electromagnetic energy, more particularly visible light energy and the substrate, e.g. alter reflected, transmitted or absorbed visible light some of which is by interference effects. Functional coatings deposited on glass substrates have always hadthe need to be aesthetically desirable for architects. Market is also keen on combining more functionalities to the optical, aesthetic and performance properties of the functionally coated glass substrate. One among the many methods of improving aesthetic quotient and value add for functionally coated glass substrates is to add patterns or decorations or advertising content to the traditional functional coating or functionally coated glass substrates.

[0007] Selective etching / removal of functional coatings is one way to achieve a patterned or textured or embossed appearance on the coated glass article. But selective removal of functional coatings is challenging due to the need for harsh chemicals. Also, selective removal of chemicals used in the process can affect other areas of the coated products and further bring about durability issues owing to the loss of functional coating in selected areas. Furthermore, safety concerns, residue effect and resistance to heat treatments are other issues popularly reported during selective etching procedures. Glass patterning and / or texturing using enamels is well known in the art. Patent publications WO 2014 / 133929 A2, US 20160118619 Al, US 20190276354 Al and WO 2022 / 190125 concerning such enameled patterned coatings are herein incorporated as reference.

[0008] The concept of ‘writable coating / selective coating’ presents an innovative approach to decorative, heat-treatable glass articles, particularly in enhancing the versatility and functionality during thermal processing. ‘Writable coating / S elective coating’ as per the teaching of the present invention is defined as coatings that enable writing and making designs / patterns on the surface of the glass substrate. Writings, designs and patterns for the purpose of this invention include but not limiting to company name / logo, dots for bird friendly glass, all aesthetically decorative design, all designs for privacy and glare reduction. Hence it would be beneficial to have a patterned or textured decorative glass article to be used for advertising and decoration by displaying patterns / signs / information for wider use in office and showroom partitioning, up-market homes,washroom basins and bath cubicles, showroom shelves, fridge shelves, doors, decorative uses, restaurant partitioning etc.

[0009] The present invention proposes the concept of a non-dissolvable, chemically treated coating to achieve visually observable distinct patterns or writings or designs or decorations. Such distinctiveness is provided by modification of the functional coating properties during thermal processing resulting in a new chemistry in some portions of the underlying coating. The other portions may be uncoated, retaining the original properties of the underlying coating.

[0010] The non-dissolvable, chemically treated coating is designed to be non-hazardous and employs neutral chemicals, ensuring that no residue is left after thermal processing. This characteristic enhances coating design options, making the process more adaptable and environmentally friendly compared to all the referenced prior art documents that rely on selectively dissolvable coatings. Prior art references often highlight selectively removable coatings that can leave residues or require extensive cleaning post-treatment, which may limit design flexibility or introduce potential contamination.

[0011] On the contrary, the present invention maintains the functionality of enabling selective treatment of specific areas during heat treatment. This capability allows for precise decorative designs and surface modifications without compromising the integrity of untreated areas. Reference to the prior art publications shows that while enabling different treatment areas is not unique, the non-dissolvable nature of this method prevents issues associated with residue, thus streamlining the process and enhancing the quality of decorative outcomes. Advantageously, the non-dissolvable, residue-free and chemically treated coatings proposed in the present invention adds a layer of durability and stability during- and post-heat treatment, supporting consistent performance under different conditions. Such improvement is not always evident in the referenced prior art publications, where the structural integrity can be compromised due to coating removal or thermal incompatibility.Thus, the present invention addresses the need in the market to develop a decorative product that is glossy, hydrophilic in nature, having improved design / aesthetic quotient in being utilized for writing, advertising, decorating etc., without compromising product performance.

[0012] SUMMARY OF THE DISCLOSURE

[0013] In one aspect the present disclosure provides a decorative article comprising a coated transparent substrate that reflects and / or transmits visible light provided with a metal solution over a portion of the coated transparent substrate. The metal solution is disposed as a pattern form to provide an etched portion of the coated transparent substrate and a non-etched portion of the coated transparent substrate and comprises salts of metals selected from sodium, copper or zinc. The decorative article is characterized in that the etched portion of the coated transparent substrate appears visually distinct from the non-etched portion of the coated transparent substrate. In another aspect the present disclosure provides a method of making a decorative article having a visually distinct patterned appearance comprising the steps of: providing a coated transparent substrate having at least one of its surface reflecting and / or transmitting visible light or having at least one of its surface absorbing and / or reflecting infrared light; providing a metal solution over at least a portion of the coated transparent substrate forming a pattern; and heat treating the article at a temperature ranging from 400 to 800°C. The metal solution chemically reacts with the underlying coated transparent substrate during the heat treatment to form etched portion of the coated transparent substrate and the coated transparent substrate free of the metal solution remains as non-etched portion of the coated transparent substrate. The method results in a decorative article with the etched portion of the coated transparent substrate appearing visually different from the non-etched portion of the coated transparent substrate.Other features and aspects of this disclosure will be apparent from the following description and the accompanying drawings.

[0014] BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Embodiments are illustrated by way of example and are not limited in the accompanying figures.

[0016] FIG. 1 illustrates a cross-sectional view of a decorative glass article 100, in accordance with one embodiment of the present invention;

[0017] FIG. 2 illustrates a cross-sectional view of the transparent substrate following the deposition of the different coatings of the present invention;

[0018] FIG. 3 illustrates a schematic of the chemical reaction between the coatings of the decorative glass article 100;

[0019] Fig. 4A demonstrates a coated glass samples before the start of the invention; and Fig. 4B demonstrates the coated sample at the end of the invention.

[0020] DETAILED DESCRIPTION

[0021] Wherever possible, the same reference numbers will be used throughout the drawings to refer to the same or the like parts. Embodiments disclosed herein are related to a decorative article having visually distinct etched and non-etched portions between one or more portions of a surface of the article for use in advertising and decoration by displaying patterns / signs / information etc. and a method for preparing the same according to the teachings of the present disclosure.

[0022] FIG. 1 illustrates a cross-sectional view of a decorative glass article 100 in accordance with one embodiment of the present disclosure. As shown, the decorative patterned glass article 100 comprises a transparent substrate 101 including a first surface 102 and a second surface 103. As illustrated in FIG. 1, an optical coating 104 is deposited over at least one surface 102 of the transparent substrate 101. The optical coating 104 is directly provided on one surface of the transparent substrate 101 covering its entiresurface area. The optical coating 104 in accordance with few embodiments of the present disclosure reflects and / or transmits visible light. The optical coating 104 in accordance with few other embodiments of the present disclosure absorbs and / or reflects infrared light.

[0023] A metal solution 105 is deposited on selected portions of the substrate 101 overlying the optical coating 104. Although metal solution 105 coating layer in FIG. 1 is depicted as the topmost coating layer on the substrate 101, additional thin film or non-thin film coating layers can be placed on top of the metal solution 105 coating layer (after thermal processing). A few of these are coloring or tinting coating layers, and selfcleaning pyrolytic coating layers as known to those skilled in the art. As shown in FIG.

[0024] 1, other portions of the substrate 101 is free of the metal solution 105 coating providing a pattern form. More particularly, the metal solution is disposed as pattern form to provide an etched portion of the coated transparent substrate and a non-etched portion of the coated transparent substrate.

[0025] The pattern form may be any pattern form including but not limited to graphic representations, text, decorative images, or a plurality of images or combinations thereof. Generally as used herein, the term ‘pattern’ refers to a design for a coating layer on the surface of a coating on a substrate. ‘Patterning’ is the process of creating the selected design or appearance form upon a surface resulting in formation of a ‘patterned’ surface.

[0026] The metal solution 105 enables selective treatment of the deposited portions of the substrate 101 during heat processing of the decorative article 100. This ability of the metal solution 105 allows for precise decorative designs and surface modifications without compromising the integrity of untreated areas i.e., portions on the surface of the optical coating on a substrate not deposited with the metal solution 105. The metal solution 105 endures various thermal processing treatments such as low-temperature processes and tempering i.e., across a wide temperature range of ~400°C to 800°C effectively without compromising performance or aesthetics. Particularly theperformance and / or aesthetics of the underlying optical coating 104 remains unaffected during the thermal processing step.

[0027] Thus, the non-dissolvable nature of the metal solution 105 coating layer during thermal processing prevents issues associated with residue, thus streamlining the process and enhancing the quality of decorative outcomes. Hence a significant advantage of the present invention is its ability to deliver customized patterns and finishes that add decorative effects without impacting the overall strength of the decorative article. The optical coating 104 comprises a magnetron sputter vacuum deposited coating, a chemical vapor deposited coating, a physical vapor deposited coating, a spray pyrolysis or a sol-gel deposited coating. The techniques of deposition of the optical coating 104 includes but not limited to sputtering, evaporation, atomic layer deposition, plasma enhanced chemical vapor deposition, spray pyrolysis. The optical coating 104 is provided on at least one surface 102 of the transparent substrate 101. The optical coating 104 as deposited on the transparent substrate 101, serves as an aesthetic addon to the glass substrate 101 and at the same time ensures thermal, visual and acoustic comfort.

[0028] The aesthetic appearance of the decorative glass articles is determined by the transmission, reflection, absorption and color coefficients or parameters of the optical coating 104 that are deposited over any transparent substrate. The coatings that are to be deposited on the transparent substrate are obtained by different ways, specifically, searching for the materials and optimizing them in order to obtain desired optical properties. Other methods include development of coatings based on the interference of different amplitudes reflected in each of the interfaces of the multilayered coatings. The transmission, reflection and absorption properties of the optical coating 104 can occur in the visible light range and / or the infrared light range. In embodiments where the absorption and / or reflection occurs in the infrared light range, the transparent substrate carries performance properties such as solar control and / or low emissivity in addition to the optical and aesthetic properties.The optical coating 104 in accordance with multiple embodiments of the present disclosure can be a single layer or comprised of a multiple layer. In either case the optical coating 104 comprises a nitride layer. In embodiments where the optical coating 104 is a multiple layer coating, the nitride layer is positioned as the outmost layer farthest from the coated surface of the transparent substrate. In all embodiments of the present invention the nitride layer is comprised of silicon, zirconium, aluminium or their combinations thereof. The nitride layer can be comprised of silicon nitride, zirconium nitride, silicon zirconium nitride or silicon aluminium nitride. In a preferred embodiment the optical coating 104 is a single layer coating made of silicon nitride. In another preferred embodiment the optical coating 104 is a multiple layer coating having silicon nitride layer as the outermost layer. In yet another embodiment of the present invention, the optical layer 104 is a carbide layer, preferably comprising silicon carbide.

[0029] Said nitride layer of the optical coating 104 in few embodiments of the present invention can be deposited by a magnetron sputter vacuum deposition, a chemical vapor deposition, a spray pyrolysis or sol-gel deposition. In other embodiments, the nitride layer of the optical coating 104 can be deposited using one of the techniques of Plasma-Enhanced Chemical Vapor Deposition (PECVD), Thermal Oxidation and Nitridation, Atomic Layer Deposition (ALD), Pulsed Laser Deposition (PLD), Laser Ablation or Low Pressure Chemical Vapor Deposition (LPCVD).

[0030] Whatever be the coating technique, the thickness of the nitride layer deposited according to the teaching of the present invention ranges between 10 nm and 500 nm. The thickness of the nitride layer plays a significant role in rate of oxidation of the layer during thermal processing. Thick layer of nitride provides an enhanced etching effect while thin layers of nitride results in a subdued etching effect. A thick nitride layer during the chemical reaction forms a thick metal silicate layer on reaction with the metal solution and thereby enhances the etching effect. With a thin nitride layer, the thickness of the metal silicate layer reduces thereby reducing the degree of etching.Further, the reaction between the metal solution and nitride layer forms a new phase that is glossy in nature. A thin nitride layer provides more reflectivity and acts as a semi-transparent anti-reflectivity layer. Whereas a thick nitride layer introduces defects and cracks because of which the reflectivity is reduced. This scenario is responsible for the gloss effect.

[0031] For the nitride layer, said metal nitride targets may also be sputtered in inert atmospheres, e.g. oxygen, or atmospheres including an inert gas, e.g. argon combined with a reactive gas, e.g., nitrogen and / or oxygen. It is possible in an alternative sense to deposit a metallic coating with subsequent nitriding.

[0032] The metal solution 105 deposited on selected portions overlying the optical the coating 104 for providing a pattern form comprises salts of metals selected from sodium, copper or zinc. In a generic embodiment, the salts of metals are selected from the group consisting of metal sulphate, metal carbonate, metal nitrate, metal hydrate, metal hydroxide and metal chlorides. In multiple embodiments of the present invention, the salts of metals are selected from the group consisting of sodium sulphate; sodium carbonate, sodium chloride, sodium nitrate, sodium hydroxide, sodium acetate trihydrate, copper sulfate pentahydrate, copper nitrate trihydrate, copper chloride dihydrate and zinc chloride. In preferred embodiments, the metal solution 105 is comprised of sodium salts. In all embodiments of the present invention, the metal solution 105 has a concentration ranging between 0.5 M and 1.5 M.

[0033] The metal solution is prepared by taking a required amount of alkali metal salt, based on the desired concentration, dissolving in water to achieve the desired volume (e.g., 100 mL). The water added may be deionized(DI) water. The solution is then stirred thoroughly until it becomes clear. Following which, a binder is added to the solution to form a paste.

[0034] In some aspects of the present invention the binder is a water-based binder.

[0035] In some aspects of the present invention the binder comprises acrylic binders, alkyd, polyurethane, silicone, epoxy based binders and combinations thereof. As anexemplary embodiment, the binder comprises acrylic, alkyd, polyurethane, silicone, epoxy- based binders and combinations thereof

[0036] The concentration of the metal solution directly impacts the oxidation rate of the nitride layer of the optical coating. At lower salt concentrations, the reaction rate is slower, resulting in more limited oxidation of the nitride layer. In contrast, at higher salt concentrations, the reaction accelerates, causing faster oxidation of nitride layer. The etched appearance further depends on the formation of intermediate species. For example, the estimated oxidation rate of silicon nitride using NaNCh at 0.2 concentration is ~290nm per 9 minutes. The oxidation rate depends on the concentration and type of salt used in the metal solution. In this case the etched appearance also depends on the formed intermediate species NaiO.

[0037] The viscosity of the paste is adjusted to be in the range of 60 sec to 150 sec using Viscometer (viscosity cup / Ford cup 4). At said viscosity the paste can be used to be overlaid on portions of the optical coating 104 in desired shape, form, design or pattern. The patterns include but not limiting to logos, lines, polka dots, circles, square, triangle, oval, rectangle, octagon, parallelogram, trapezoid, pentagon, hexagon, stars, gradients, abstract shapes or a combination thereof, with varying diameters and depths. Patterns according to the teachings of the present invention also refers to writing, advertising, decorating, displaying information etc., The surface area to be covered by the metal solution 105 in the present disclosure is varied based on the desired pattern.

[0038] The metal solution 105 is provided at a thickness ranging between 1 p and 3p. Various conventionally known techniques can be used for the coating of the metal solution 105. Such techniques include not limiting to spray coating, screen printing, digital printing, bar coating, spin coating, sip coating, drop casting, doctor blade coating or bar coating. Following the sequential deposition of the optical coating 104 and the transparent metal coating 105, the transparent substrate 101 is subjected to thermal processing. Thermal treatments such as low-temperature processes and tempering are carried out resulting in a heat-treatable decorative glass article 100. A wide temperature range of ~400°C to800°C are suitable for the thermal processing. The optical coating 104 and the transparent metal coating 105 both withstand the preferred temperatures ranging between ~400°C to 630 °C, wherein the optical, performance and aesthetics properties of the glass article remains uncompromised. The coating is designed to be non-hazardous and employs neutral chemicals, ensuring that no residue is left after the heat treatment process. This characteristic enhances coating design options, making the process more adaptable and environmentally friendly compared to existing prior art that rely on selectively dissolvable coatings. Since the prior art often selectively dissolve coatings, the burning step typically leaves residues or require extensive cleaning post thermal processing, which may limit design flexibility or introduce potential contamination.

[0039] The invention maintains the functionality of enabling selective treatment of specific areas during heat treatment. This capability allows for precise decorative designs and surface modifications without compromising the integrity of untreated areas i.e., portions of the optical coating 104 not overlaid with the metal solution 105.

[0040] The visually observable pattern results from the visible contrast between the metal solution 105 free portionsl20 of the substrate 101 and the metal solution 105 coated surface portion 110 of the substrate.

[0041] Schematics of the chemical reaction occurring during the thermal processing of the decorative article is shown in Fig. 2. The presence of oxidation environment during the heat processing step leads to the formation of SiO2resulting from oxidation of the nitride layer of the optical coating 104. For example, a nitride layer made of silicon nitride undergoes the following reaction:

[0042]

[0043] In the next step the presence of metal in the metal solution 105 coating causes absorption of the metallic vapours on the silica surface leading to oxide formation of the metal salts. For example, a metal solution comprising sodium sulfate undergoes the following reaction to form sodium oxide:

[0044]

[0045] Formation of liquid Silicides destroy the protective surface oxides leading to accelerated corrosion at high Temp °C ranges captured by the reaction:

[0046] Na2O + SiO2-> Na2SiO3(3)

[0047] As shown in Fig. 3 the sequence of reactions during the thermal processing is as follows:

[0048] Diffusion of oxygen through the liquid phase (1)

[0049] Oxidation of oxynitride to silica (2)

[0050] Outward diffusion of product gas N2(3)

[0051] Thus the above listed chemical reactions taking place during the thermal processing step results in distinctive appearance of portions coated with the metal solution 105 and portions not coated with the metal solution 105. The portions not coated with the metal solution 105 retain the optical characteristics of the optical coating 104. Reason being the coating is unaffected by the oxidation, hence retaining its coating characteristics. These reactions modify the coating’s properties, resulting in a new chemistry that can be utilized for patterning including but not limited to advertising or writing or printing or displaying information on the coated article.

[0052] Application of the transparent metal coating 105 on the optical coating 104 and subsequently tempering, oxidizing the transparent substrate with stack top material, result in a decorative article that is glossy and having a hydrophilic nature. Said decorative article is heat-treatable, particularly in enhancing the versatility and functionality during thermal processing. The invention deals with non-dissolvable, chemically treated coating involving non-hazardous, neutral chemicals, ensuring that no residue is left after the heat treatment process.

[0053] The invention also discloses a method of providing a decorative article according to the teaching of the present invention having a visually distinct patterned appearance comprising the following steps.Firstly, providing a coated transparent substrate having at least one of its surface reflecting and / or transmitting visible light or having at least one of its surface absorbing and / or reflecting infrared light. Such coating called the optical coating according to the present invention is deposited using one of the techniques of Plasma-Enhanced Chemical Vapor Deposition (PECVD), Thermal Oxidation and Nitridation, Atomic Layer Deposition (ALD), Pulsed Laser Deposition (PLD), Laser Ablation or Low Pressure Chemical Vapor Deposition (LPCVD).

[0054] Secondly, providing a metal solution over at least a portion of the coated transparent substrate forming a pattern. The metal solution is prepared by taking a required amount of alkali metal salt, based on the desired concentration, dissolving in in water to achieve the desired volume (e.g., 100 mL).The water added may be deionized(DI) water. The solution is then stirred thoroughly until it becomes clear. Following which, a waterbased binder is added to the solution to form a paste. As an exemplary embodiment, such water-based binder include not limiting acrylic binders, silicone-based binders. The concentration of the metal solution directly impacts the glossiness, color contrast of the decorative glass article. Not to mention highly concentrated metal solutions are prone to solubility issues.

[0055] The viscosity of the paste is adjusted to be in the range of 60 sec to 150 sec using viscometer (viscosity cup / Ford cup). At said viscosity the paste can be used to be overlaid on portions of the optical coating 104 in desired shape, form, design or pattern. Coating techniques selected from the group consisting of spray coating, screen printing, digital printing, bar coating, spin coating, sip coating, drop casting, doctor blade coating or bar coating can be used for depositing the metal solution on the coated substrate. In the final step, the coated substrate is heat treated at a temperature ranging between 400 and 800°C that produces the oxidation environment for the metal solution to chemically react with the underlying optical coating to form etched portion of the coated transparent substrate. The coated transparent substrate free of the metal solution remains as non-etched portion of the coated transparent substrate. The etched portionof the coated transparent substrate appears visually different from the non-etched portion of the coated transparent substrate.

[0056] A significant advantage of this method is its ability to deliver customized patterns and finishes that add decorative effects without impacting the overall strength of the glass. In contrast, prior art might achieve decorative effects but can suffer from aesthetic limitations or require additional processing to enhance the finish. The method results in vibrant decorative outcome, surpassing the aesthetic results often seen in published data where residue or coating degradation may dull the final appearance.

[0057] The portions having the metal solution following the thermal processing step has a distinct reflection, absorption and / or transmission properties compared to the remaining portions of the substrate not coated with the metal solution resulting in a visual distinctiveness. This distinction achieves greater contrast of the coated glass substrate.

[0058] EXAMPLES

[0059] Following examples are given by way of illustration therefore should not be construed to limit the scope of the invention.

[0060] Preparation of Metal solution

[0061] For the preparation of the metal salt solution, the required amount of the metal salt, based on the desired concentration, was weighed and dissolved in water to achieve the desired volume (e.g., 100 mL). The water added may be deionized water(DI). The solution was then stirred thoroughly until it became clear. Following this, a water-based binder was added to the solution to form a paste. Preparation of a coated substrate with optical coating

[0062] Coated products manufactured by Saint-Gobain under the names SCN 145 and STR were taken as samples and the prepared transparent metal salt solutions were appliedon the surface of these samples in a patterned form. Said products SCN 145 and STR comprise of optical coatings that have a silicon nitride layer.

[0063] This silicon nitride layer in portions overlaid with the metal solution reacts with the metal solution in a manner described as the teaching of the present invention to form an etched appearance during thermal processing step. Fig. 4 A and 4B demonstrates photographs of the samples prepared as per the teaching of the invention, post thermal processing step. Fig. 4 A demonstrates a coated glass samples before the start of the invention. Fig. 4B demonstrates the coated sample at the end of the invention, where a clear demarcation of the etched portion which was overlaid with the metal solution and the non-etched portion free of the metal solution coating can be seen. The difference in the contrast when viewing from the glass side is clearly visible.

[0064] Testing of optical characteristic post thermal processing

[0065] The performance of the coated substrates was tested after etching of its surface using the invention. The optical properties of the metal solution 105 free portions 120 of the substrate and the metal solution 105 coated surface portion 110 of the substrate were measured and tabulated in Table 1. The measurements tabulated under ‘Etched side’ refers to the metal solution 105 coated surface portion 110 and measurements tabulated under ‘Non-etched side’ refers to the metal solution 105 free portions 120.

[0066] Table 1 : Optical Measurements

[0067]

[0068] From Table 1 it can be understood that the optical characteristics of the etched and nonetched portions are distinct and these result in distinctive appearance between the etched and non-etched portions of the substrate.

[0069] The decorative glass substrate according to this disclosure may have various applications. The patterned decorative article obtained in accordance with the present disclosure may, for example be used for various interior applications of buildings including but not limited to wardrobes, as doors and windows for furniture, as partitions, in tables, shelves, in bathrooms, in shops displays, as wall covering or as spandrels. Hence can be used for decorative purposes as not limiting to a wall mount in office spaces, lift lobbies, receptions, kitchens, bathrooms and could also be possibly used as dinning and coffee table surfaces. More and more of these applications necessitate the glass article to achieve both aesthetic appeal to customers, and functional performance.

[0070] Additionally, the decorative glasses prepared according to the teaching of the invention can be used as bird safety glasses wherein the patterned obtained on the glass reduces bird collision when windows are installed with such glasses.

[0071] Note that not all of the activities described above in the general description or the examples are required, that a portion of a specific activity may not be required, and that one or more further activities may be performed in addition to those described. Still further, the order in which activities are listed is not necessarily the order in which they are performed.

[0072] Benefits, other advantages, and solutions to problems have been described above with regard to specific embodiments. However, the benefits, advantages, solutions to problems, and any feature(s) that may cause any benefit, advantage, or solution to occur or become more pronounced are not to be construed as a critical, required, or essential feature of any or all the claims.The specification and illustrations of the embodiments described herein are intended to provide a general understanding of the structure of the various embodiments. The specification and illustrations are not intended to serve as an exhaustive and comprehensive description of all of the elements and features of apparatus and systems that use the structures or methods described herein. Certain features, that are for clarity, described herein in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features that are, for brevity, described in the context of a single embodiment, may also be provided separately or in a sub combination. Further, reference to values stated in ranges includes each and every value within that range. Many other embodiments may be apparent to skilled artisans only after reading this specification. Other embodiments may be used and derived from the disclosure, such that a structural substitution, logical substitution, or another change may be made without departing from the scope of the disclosure. Accordingly, the disclosure is to be regarded as illustrative rather than restrictive.

[0073] The description in combination with the figures is provided to assist in understanding the teachings disclosed herein, is provided to assist in describing the teachings, and should not be interpreted as a limitation on the scope or applicability of the teachings. However, other teachings can certainly be used in this application.

[0074] As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having" or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a method, article, or apparatus that comprises a list of features is not necessarily limited only to those features but may include other features not expressly listed or inherent to such method, article, or apparatus. Further, unless expressly stated to the contrary, "or" refers to an inclusive-or and not to an exclusive-or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).Also, the use of "a" or "an" is employed to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be read to include one or at least one and the singular also includes the plural, or vice versa, unless it is clear that it is meant otherwise. For example, when a single item is described herein, more than one item may be used in place of a single item. Similarly, where more than one item is described herein, a single item may be substituted for that more than one item.

[0075] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The materials, methods, and examples are illustrative only and not intended to be limiting. To the extent that certain details regarding specific materials and processing acts are not described, such details may include conventional approaches, which may be found in reference books and other sources within the manufacturing arts.

[0076] While aspects of the present disclosure have been particularly shown and described with reference to the embodiments above, it will be understood by those skilled in the art that various additional embodiments may be contemplated by the modification of the disclosed machines, systems and methods without departing from the spirit and scope of what is disclosed. Such embodiments should be understood to fall within the scope of the present disclosure as determined based upon the claims and any equivalents thereof.List of Elements

[0077] 100 -Decorative glass article

[0078] 101 - Transparent substrate

[0079] 102 - First surface and coating side view 103 - Second surface

[0080] 104 - Optical coating

[0081] 105 - Transparent Metal Coating

[0082] 110 - Metal solution coated portion 120 - Metal solution free portion

Claims

Claims1) A decorative article comprisinga coated transparent substrate that reflects and / or transmits visible light provided with a metal solution over a portion of the coated transparent substrate,wherein the metal solution being disposed in a pattern form to provide an etched portion of the coated transparent substrate and a non-etched portion of the coated transparent substrate,wherein the metal solution comprises salts of metals selected from sodium, copper or zinc and characterized in that the etched portion of the coated transparent substrate appears visually distinct from the non-etched portion of the coated transparent substrate.2) The decorative article as claimed in claim 1 , wherein the metal solution has a concentration ranging from 0.5 M to 1.5 M.3) The decorative article as claimed in claim 1, wherein the salts of metals are selected from the group consisting of metal sulphate, metal carbonate, metal nitrate, metal hydrate, metal hydroxide and metal chlorides.4) The decorative article as claimed in claim 3, wherein the salts of metals are selected from the group consisting of sodium sulphate; sodium carbonate, sodium chloride, sodium nitrate, sodium hydroxide, sodium acetate trihydrate, copper sulfate pentahydrate, copper nitrate trihydrate, copper chloride dihydrate and zinc chloride.5) The decorative article as claimed in claim 1, wherein the metal solution comprises water and a binder.6) The decorative article as claimed in claim 5, wherein the binder is selected from a group consisting of, but not limited to acrylic, alkyd, polyurethane, silicone, epoxy-based binders and combinations thereof.7) The decorative article as claimed in claim 1, wherein the metal solution is provided at a thickness ranging between 1 p and 3p and is transparent in nature.8) The decorative article as claimed in claim 1, wherein the coated transparent substrate comprises a magnetron sputter vacuum deposited coating, a chemical vapor deposited coating, a physical vapor deposited coating, a spray pyrolysis or sol-gel deposited coating.9) The decorative article as claimed in claim 8, wherein the coating comprises a single layer coating comprising a nitride layer or a multiple layer coating comprising a nitride layer as the outmost layers farthest from the coated surface.10) The decorative article as claimed in claim 8, wherein the coating comprises a carbide layer.11) The decorative article as claimed in claim 9, wherein the nitride layer is comprised of silicon, zirconium, aluminium or their combinations thereof. 12) The decorative article as claimed in claim 10, wherein the carbide layer comprises silicon carbide.13) The decorative article as claimed in claim 9 or claim 10, wherein the nitride or carbide layer has a thickness ranging between 10 nm and 500 nm.14) The decorative article as claimed in claim 1, wherein the metal solution chemically reacts with the coated transparent substrate to form the etched portion of the coated transparent substrate.15) The decorative article as claimed in claim 1, wherein the non-etched portion of the coated transparent substrate is free of metal solution.16) The decorative article as claimed in claim 1, wherein the coated transparent substrate absorbs and / or reflects infrared light.17) The decorative article as claimed in claim 1 is heat treated.18) A method of providing a decorative article as claimed in claim 1 having a visually distinct appearance comprising the steps of:providing a coated transparent substrate having at least one of its surface reflecting and / or transmitting visible light or having at least one of its surface absorbing and / or reflecting infrared light;providing a metal solution over at least a portion of the coated transparent substrate forming a pattern; andheat treating the article at a temperature ranging from 400 to 800°C, wherein the metal solution chemically reacts with the underlying coated transparent substrate during the heat treatment to form etched portion of the coated transparent substrate; wherein the coated transparent substrate free of the metal solution remains as non-etched portion of the coated transparent substrate and wherein the etched portion of the coated transparent substrate appears visually different from the non-etched portion of the coated transparent substrate.19) The method of providing a decorative article as claimed in claim 18, wherein the metal solution is prepared by dissolving the metal salt in water and a binder.20) The method of providing a decorative article as claimed in claim 18, wherein the metal solution is provided using a coating technique selected from the group consisting of spray coating, screen printing, digital printing, bar coating, spin coating, sip coating, drop casting, doctor blade coating or bar coating.21) The method of providing a decorative article as claimed in claim 18, wherein the coating of the transparent substate is provided by a magnetron sputter vacuum deposition, a chemical vapor deposition, a spray pyrolysis or sol-gel deposition1

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