Process for coating integrated patterning and functionalization of glass and use thereof

Abstract

The present disclosure relates to a process for functionalizing a glass. A process for producing a patterned functional coating on a glass surface. In particular, the present disclosure provides a process for integrating an integrated, embedded, and non-peelable functionalized powder coating onto a glass surface by CO2 laser patterned line scan irradiation. The invention also relates to the use of the functionalized glass in various applications.

Description

Technical Field

[0001] The present disclosure relates to a process for functionalizing glass substrates. Specifically, the process can produce patterned functional coatings on glass surfaces. In particular, the present disclosure provides a process for integrating an integrated, embedded, and non-strippable functionalized powder coating onto a glass surface using patterned line scanning CO2 laser irradiation. The present disclosure also relates to the use of the functionalized glass substrates in various applications, such as energy storage glass, keeping a room warm or cool depending on the materials integrated into the glass, integration of wiring and connections, reflection and absorption of specific radiation, magnetism, spintronics, advanced sensors, actuators, and the like. Background Art

[0002] The background description includes information that may be useful in understanding the present invention. No admission is made that any of the information provided herein is prior art or relevant to the present invention, or that any publication specifically or implicitly referenced is prior art.

[0003] Glass has traditionally been used as a building material or passive support material in several technical applications. There are cases where glass is doped with specific elements during its formation to make it functional. Laser engraving of glass is also performed using lasers of different wavelengths for different applications.

[0004] However, there have been few attempts to treat glass surface layers using different forms of energy treatments, whereby functional materials of interest for emerging technologies can be directly surface-incorporated into the glass surface layer.

[0005] In fact, the associative and reactive integration of such materials onto glass surface layers can generate entirely new materials and phases with hitherto unrealized compositions, structures and properties.

[0006] This has the potential to significantly open up and enhance the applicability of prefabricated glasses (which are otherwise used as passive support materials) in application areas such as energy, magnetism, spintronics, advanced sensors and actuators, etc.

[0007] Thus, disclosed herein is the development of processes that can expand the application prospects of glass through synergistic binding and reactive integration of glass with other functional materials, particularly in powder form.

[0008] Purpose of the present invention

[0009] The object of the present invention is to provide a process for functionalizing a glass substrate.

[0010] The object of the present invention is to provide a process for producing patterned functional coatings on glass surfaces.

[0011] Another object of the present invention is to provide a process for integrating an integrated, embedded and non-strippable functionalized powder coating onto a glass surface by CO2 laser patterned line scanning irradiation.

[0012] Yet another object of the present invention is to provide functionalized glass for various applications through the process disclosed herein. Summary of the Invention

[0013] This Summary is provided to introduce a selection of concepts in a simplified form that are further described below in the Detailed Description. This Summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used as an aid in determining the scope of the claimed subject matter.

[0014] In one aspect, a process for manufacturing a functionalized glass substrate is provided, the process comprising the following steps in sequence:

[0015] i) providing a glass substrate,

[0016] ii) etching the surface of the glass substrate to form an etched surface,

[0017] iii) contacting at least a portion of the etched surface with a material,

[0018] iv) laser processing the portion of the etched surface and / or the material to form a functionalized glass substrate, wherein:

[0019] (a) incorporating the material or its derivative into the glass substrate, and / or

[0020] (b) a coating comprising said material or a derivative thereof on said portion of the etched surface.

[0021] It has surprisingly been determined that the process of the present invention allows for the associative and reactive integration of materials within a glass substrate.

[0022] Etching the surface of the glass substrate in step ii) may be performed by laser treatment and / or chemical treatment, preferably by laser treatment.

[0023] When present, the laser treatment of step ii) can be performed using a gas laser, a chemical laser, a dye laser, a metal-vapor laser, a solid-state laser, and / or a semiconductor laser. Preferably, when present, the laser treatment of step ii) is performed using a gas laser such as a xenon ion laser, a nitrogen laser, a krypton laser, a helium-neon laser, an excimer laser, a carbon monoxide laser, a carbon dioxide laser, and / or an argon laser. Most preferably, when present, the laser treatment of step ii) is performed using a carbon dioxide laser. The carbon dioxide laser preferably emits at 9-11 μm, more preferably at 10.6 μm.

[0024] When present, the laser treatment of step ii) can be performed using a laser power of 1 to 50 W, more preferably 1 to 40 W, even more preferably 1 to 30 W. When present, the laser treatment of step ii) can be performed using a laser scanning speed of 1 mm / s to 10,000 mm / s, more preferably 1 mm / s to 5,000 mm / s, even more preferably 1 mm / s to 1,000 mm / s, and most preferably 10 mm / s to 500 mm / s. The laser treatment can be performed in continuous wave, pulsed, scanning, or any other suitable mode.

[0025] The laser treatment in step iv) can be performed using a gas laser, a chemical laser, a dye laser, a metal-vapor laser, a solid-state laser, and / or a semiconductor laser. Preferably, the laser treatment in step iv) is performed using a gas laser (such as a xenon ion laser, a nitrogen laser, a krypton laser, a helium-neon laser, an excimer laser, a carbon monoxide laser, a carbon dioxide laser, and / or an argon laser). Most preferably, the laser treatment in step iv) is performed using a carbon dioxide laser. The carbon dioxide laser preferably emits at 9-11 μm, more preferably at 10.6 μm.

[0026] The laser treatment in step iv) can be performed using a laser power of 1 to 50 W, more preferably 1 to 40 W, and even more preferably 1 to 30 W. The laser treatment in step iv) can be performed using a laser scanning speed of 1 mm / s to 10,000 mm / s, more preferably 1 mm / s to 5,000 mm / s, even more preferably 1 mm / s to 1,000 mm / s, and most preferably 10 mm / s to 500 mm / s. The laser treatment can be performed in continuous wave, pulsed, scanning, or any other suitable mode.

[0027] When present, the chemical treatment of step ii) may be performed using hexafluorosilicic acid, hydrogen fluoride, hydrofluoric acid, sodium fluoride and / or ferric chloride.

[0028] Etching the surface of the glass substrate in step ii) may form a pattern on the surface of the glass substrate. Preferably, the pattern comprises parallel lines, more preferably comprises a grid.

[0029] Preferably, the material of step iii) is in solid form, more preferably in powder form, or in the form of a film that adheres to the portion of the etched surface. When the material of step iii) is in the form of a film that adheres to the portion of the etched surface, preferably, the film has been deposited as a liquid and then dried to form a solid film, for example, by spray pyrolysis, chemical bath deposition, or sol-gel techniques. Alternatively, the film may be deposited via other suitable methods, such as chemical vapor deposition, electroplating, sputtering, or evaporation techniques.

[0030] The material of step iii) and / or its material or derivative incorporated into the glass substrate in step iv) and / or the material or derivative of the coating on the portion of the etched surface in step iv) may include particles having a z-average diameter of at least about 1 nm, 10 nm, 50 nm, 100 nm, 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1000 nm, 1100 nm, 1200 nm, 1300 nm, 1400 nm, 1500 nm, 1600 nm, 1700 nm, 1800 nm, 1900 nm, 2000 nm, 2500 nm, 3000 nm, 4000 nm, 5000 nm, 6000 nm, 7000 nm, 8000 nm or at least 9000 nm according to ISO 22412:2017. In some embodiments, the particles may have a z-average diameter of less than 10000 nm, 9000 nm, 8000 nm, 7000 nm, 6000 nm, 5000 nm, 4500 nm, 4000 nm, 3500 nm, 3000 nm, 2500 nm, 2000 nm, 1900 nm, 1800 nm, 1700 nm, 1600 nm, 1500 nm, 1400 nm, 1300 nm, 1200 nm, 1100 nm, 1000 nm, 900 nm, 800 nm, 700 nm, 600 nm, 500 nm, 250 nm, or less than 100 nm according to ISO 22412:2017. The z-average diameter of the particles can range from any minimum value to any maximum value recited above, for example, 1 nm to 10,000 nm, 50 nm to 5,000 nm, 100 nm to 2,500 nm, 200 nm to 2,000 nm, or 500 nm to 1,000 nm.

[0031] The material of step iii), and / or the material or its derivative incorporated into the glass substrate in step iv), and / or the material or its derivative of the coating on the portion of the etched surface in step iv) may include an inorganic material, a polymer, an organic molecule, an organic-inorganic hybrid material, or the like, or any combination thereof. Preferably, the material includes one or more metals, metal oxides, nitrides (e.g., TiN, BN, etc.), sulfides (e.g., MOS2, BaS, etc.), and / or halides, such as chlorides (e.g., NaCl, CuCl, CoCl, etc.) or bromides (e.g., CuBr, etc.). The material may include one or more of Fe, Mn, Ni, Sn, Zn, Fe2O3, TiO2, Ag2O, LCO (lithium cobalt oxide), NaWO4, ZrO2, TiN, BN, CuO, CuCl, CuBr, NaCl, CoCl, BaS, and / or MoS2. The material may include a mixture of materials, for example, the material may include Fe and CuCl, or TiO2 and CuCl, or TiO2 and Sn, or TiO2 and BN, or NaCl and Ni. The material may be a combination of metals, oxides, nitrides, sulfides, etc., and is not limited to those given above, but may also include a wide range of other categories (e.g., superconducting materials, thermoelectric materials, polymer materials, etc.).

[0032] Preferably, in step iii), the material is provided as a layer on the etched surface. Preferably, the material contacts at least 50%, more preferably 70%, even more preferably 90%, even more preferably substantially all, and most preferably all of the etched surface. In some embodiments, the layer can be provided in different areas of the etched surface, for example, in areas where etching has already occurred. Preferably, the material layer on the etched surface has a thickness of 10 μm to 100 μm, more preferably 1 nm to 10 μm.

[0033] When viewed perpendicular to the etched surface of the glass substrate, the material or its derivative incorporated within the glass substrate is preferably up to 50 μm from the etched surface, more preferably up to 25 μm from the etched surface, even more preferably up to 20 μm from the etched surface, and most preferably up to 20 μm to up to 10 μm from the etched surface. The material or its derivative incorporated within the glass substrate may form a gradient in its frequency when moving perpendicularly from the etched surface.

[0034] The laser treatment of step iv) can result in a reduction of material.

[0035] The process can be performed in an air atmosphere or an inert atmosphere.

[0036] Preferably, step iv) further comprises ultrasonically treating the functionalized glass substrate. The ultrasonic treatment can be performed in a suitable organic or aqueous solvent. Preferably, after the ultrasonic treatment of the functionalized glass substrate, the functionalized glass substrate is dried using a hot air blower or an oven.

[0037] In one embodiment, the present disclosure relates to a process for functionalizing the surface of a glass substrate by a CO2 laser (wavelength 10.6 μm) direct write patternable transient photothermal process in a scanning mode (x, y or x and y) for the integrated and reactive bonding of powder coating layers on the glass surface.

[0038] In one embodiment of the present disclosure, powder is spread on the etched glass surface rather than through a traditional coating process that involves precursor materials pumped from a nozzle for coating.

[0039] In one embodiment of the present disclosure, the solution provided by the present invention is in the form of scanned CO2 laser beam processing of a glass surface coated with one or more functional materials, whereby the transient heat pulse presented by the scanned laser beam achieves the combined and reactive integration of the two.

[0040] In yet another embodiment of the present disclosure, derivatives of the functionalized glass substrate may have different properties (eg, electronic, chemical, and mechanical) compared to the material.

[0041] Preferably, the surface of the glass substrate is a major surface of the glass substrate. Preferably, the glass substrate is transparent. The glass substrate can be a transparent metal oxide-based glass pane. Preferably, the glass pane is a clear float glass pane, preferably a low-iron float glass pane. Clear float glass refers to glass having a composition as defined in BS EN 572-1 and BS EN 572-2 (2004). For clear float glass, the Fe2O3 weight level is typically 0.11%. Float glass having an Fe2O3 content of less than about 0.05% by weight is typically referred to as low-iron float glass. This glass typically has the same basic composition as the other component oxides, i.e., low-iron float glass is also soda-lime-silica glass, such as clear float glass. Typically, the Fe2O3 content of low-iron float glass is less than 0.02% by weight. Alternatively, the glass pane is a borosilicate-based glass pane, an alkali-aluminosilicate-based glass pane, or an alumina-based crystalline glass pane.

[0042] According to a second aspect of the present invention, there is provided use of a functionalized glass substrate manufactured according to the process of the first aspect in architectural, automotive or electronic applications, for example in glass window frames, walls, partitions, shutters, doors, electronic devices (such as PV modules, liquid crystal displays or OLEDs), touch screens, mirrors, containers, furniture, splashbacks, car windows, energy storage glass, electrical connectors, sensors, actuators, magnetic devices and / or spintronic devices.

[0043] Various objects, features, aspects and advantages of the present subject matter will become more apparent from the following detailed description of preferred embodiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] The characteristics and advantages of the subject matter as disclosed in the present disclosure will become more apparent from the detailed description of embodiments thereof, given purely by way of example, with reference to the accompanying drawings, in which:

[0045] Figure 1A : Flowchart of the process according to the present invention.

[0046] Figure 1B : Glass substrate etched along x and y directions by CO2 laser line scanning; Figure 1C : In-plane interface region of the etched glass substrate and the integrated membrane (top view or surface view).

[0047] Figure 2 : XRD of integrated fused Fe powder coating on glass surface.

[0048] Figure 3 : FE-SEM images of embedded or integrated functionalized Fe powder coatings after CO2 laser irradiation.

[0049] Figure 4 : XRD of a silver oxide powder coating on a glass surface treated with a CO2 laser. The powder has been converted into a nanosilver film.

[0050] Figure 5 : FESEM morphology: Nanosilver film from Ag2O powder on glass.

[0051] Figure 6 : XRD analysis reveals the formation of rutile (black) phase thin films with oxygen vacancy defects from the initial anatase TiO2.

[0052] Figure 7 : FESEM image of rutile TiO2 thin film on glass surface.

[0053] Figure 8 : XRD of laser-treated Sn powder coating, showing the formation of mixed phase of Sn and SnO2.

[0054] Figure 9 : FESEM analysis revealed that continuous and dense Sn and SnO2 films were formed by CO2 laser treatment.

[0055] Figure 10 : XRD of Fe3O4 black film integrally bonded on glass surface by CO2 laser treatment of hematite (Fe2O3) coated glass.

[0056] Figure 11 : XRD of copper (I) oxide (Cu2O) coating produced by CO2 laser treatment of copper (II) oxide (CuO) powder coating on glass. DETAILED DESCRIPTION

[0057] The following is a detailed description of embodiments of the present disclosure. The embodiments are disclosed in detail to clearly convey the present disclosure. However, the amount of detail provided is not intended to limit the expected variations of the embodiments; on the contrary, it is intended to cover all modifications, equivalents, and alternatives that fall within the spirit and scope of the present disclosure as defined by the appended claims.

[0058] All publications herein are incorporated by reference to the same extent as if each individual publication or patent application was specifically and individually indicated to be incorporated by reference. To the extent that a definition or use of a term in an incorporated reference is inconsistent or contrary to the definition of that term provided herein, the definition of that term provided herein applies and the definition of that term in the reference does not apply.

[0059] Reference throughout this specification to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment. Thus, the phrases "in one embodiment" or "in an embodiment" appearing in various places throughout this specification are not necessarily referring to the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.

[0060] In some embodiments, numerals have been used to quantify weight percentages, angles, etc. to describe and claim certain embodiments of the present invention, and should be understood as being modified by the term "about" in some cases. Therefore, in some embodiments, the numerical parameters set forth in the written description and the appended claims are approximate values, which can vary depending on the desired properties sought to be obtained in a particular embodiment. In some embodiments, numerical parameters should be interpreted according to the number of reported significant figures and by applying common rounding techniques. Although the numerical ranges and parameters setting forth the wide range of some embodiments of the present invention are approximate values, the numerical values set forth in the specific examples are reported as accurately as possible. The numerical values presented in some embodiments of the present invention may contain certain errors, which are necessarily caused by the standard deviation found in their respective test measurements.

[0061] Various terms used herein are shown below. To the extent a term used in a claim is not defined below, it should be given the broadest definition persons in the pertinent art have given that term at the time of filing, as reflected in printed publications and issued patents.

[0062] As used in the description herein and the appended claims, the meaning of "a," "an," and "the" includes plural references unless the context clearly dictates otherwise. Also, as used in the description herein, the meaning of "in" includes "in" and "on" unless the context clearly dictates otherwise.

[0063] Unless the context requires otherwise, throughout the following specification, the word "include" and variations thereof (such as "includes" and "comprising") should be interpreted as having an open, inclusive meaning, such as "including but not limited to."

[0064] The description of numerical ranges herein is intended only to serve as a shorthand method of individually quoting each individual value falling within the range. Unless otherwise indicated herein, each individual value is incorporated into the specification as if it were individually recited herein. In the discussion of the invention herein, unless otherwise indicated to the contrary, the disclosure of alternative values for the upper or lower limits of the permitted ranges for parameters (together with an indication that one of the values is more highly preferred than another) will be interpreted as an implicit statement that each intermediate value of the parameter between the more preferred and less preferred values in the alternative is itself preferred over the less preferred value, and is also preferred over each value between the less preferred value and the intermediate value.

[0065] All methods described herein can be performed in any suitable order unless otherwise indicated herein or clearly contradicted by the context. The use of any and all examples or exemplary language (e.g., "such as") provided with respect to certain embodiments herein is intended only to better illustrate the present invention and does not limit the scope of the invention as otherwise claimed. Any language in the specification should not be construed as indicating any unclaimed element that is essential to the practice of the present invention.

[0066] The grouping of the alternative elements of the present invention disclosed herein or embodiment should not be construed as limiting. Each group member can quote and claim protection individually or in any combination with other members of the group or other elements found herein. For convenience and / or patentability, one or more members of the group can be included in the group or deleted from the group. When any such inclusion or deletion occurs, the description is considered to the group comprising modification in this article.

[0067] The following description and the embodiments described therein are provided by way of one or more examples of specific embodiments illustrating the principles and aspects of the present disclosure. These examples are provided to illustrate, not to limit, these principles and the present disclosure.

[0068] The titles and abstracts of the inventions provided herein are for convenience only and do not interpret the scope or meaning of the embodiments.

[0069] The following discussion provides many example embodiments of the subject matter of the present invention. Although each embodiment represents a single combination of elements of the present invention, the subject matter of the present invention is considered to include all possible combinations of the disclosed elements. Therefore, if one embodiment includes elements A, B, and C, and a second embodiment includes elements B and D, then even if not clearly disclosed, the subject matter of the present invention is also considered to include other remaining combinations of A, B, C, or D.

[0070] Various terms are used herein. To the extent a term used in a claim is not defined below, it should be given the broadest definition persons in the pertinent art have given that term at the time of filing, as reflected in printed publications and issued patents.

[0071] In the context of the present invention, a "derivative" is a chemical substance that is structurally related to another chemical substance and can theoretically be derived from it.

[0072] In the context of the present invention, for any given location at a surface of a layer, the "thickness" of a layer is represented by the distance through the layer in the direction of its smallest dimension from that location at the surface of the layer to a location at the opposite surface of the layer.

[0073] While particular forms of the invention have been shown and described, it will be apparent that various modifications can be made without departing from the spirit and scope of the invention.

[0074] Embodiments of the present disclosure relate to processes for producing patterned functional coatings for glass layers. In particular, the present disclosure provides a process for integrating an integrated, embedded, and non-strippable functionalized powder coating onto a glass surface using patterned line scanning CO2 laser irradiation. The present disclosure also relates to the use of the functionalized glass in various applications.

[0075] In one embodiment, the present disclosure provides a solution in the form of scanning CO2 laser beam treatment of a glass surface coated with one or more functional materials, whereby transient heat pulses presented by the scanning laser beam achieve associative and reactive integration of the two. This method simultaneously heats both the glass surface and the coated powder material, enabling rapid diffusion bonding with the wrought material and reaction between the materials. The "associative" aspect further distinguishes the present invention from conventional surface coating methods, in which the glass and coating retain their own identities and properties.

[0076] In one embodiment of the present disclosure, functionalization is achieved by a direct-write patternable transient photothermal process based on a CO2 laser (wavelength 10.6 μm) in a scanning mode (x, y or x and y) for the integrated and reactive bonding of powder coating layers on the surface of glass.

[0077] In one embodiment of the present disclosure, the CO2 laser power and the scanning speed may be in the range of 1 W to 30 W and 1 mm / s to 1000 mm / s, respectively, but are not limited to these intervals.

[0078] According to the present embodiment, various types of material powders (such as metal powders, metal oxides, nitrides, carbides, chlorides, sulfides, etc.) can be used to achieve integrated and / or reactively bonded uniform or patterned coatings on the glass surface. In addition, mixed powders of metals and metal oxides, chlorides, nitrides, sulfides, etc. can also be integrated into the glass surface, making it possible to obtain compounds or composite layers with engineering application value on the surface. The combination of powders can be wide; for example, mixed metal / semi-metal oxides, oxides with another oxide, metals with another metal, oxides with nitrides or chlorides, etc. The thickness (or multiple thicknesses) of the material (material layer) used as a coating before laser treatment determines the laser energy density and scanning speed to achieve a desired set of properties and a gradient of material composition as a function of depth.

[0079] As described above, the process according to the present invention is shown as Figure 1A, and comprises the following steps: patterned etching of the glass surface by a CO2 laser, followed by uniform spreading of the desired precursor powder coating, and laser irradiation of the coated surface (without any medium other than the atmosphere / environment) again in line scan mode under normal atmospheric conditions in a single or multiple scan mode with or without or partial scan overlap in the x and / or y direction. The process may also include the following steps: ultrasonic treatment of the functionalized glass in a suitable solvent / water, followed by drying with a hot air blower / oven. The precursor powder is selected from materials that are metals / metal oxides, nitrides, sulfides and chlorides and / or combinations thereof. The use of a CO2 laser in a scanning mode is important because it imparts transient heating at any local spot, and the laser itself can be operated in CW or pulsed mode, presenting different results in terms of the final material obtained and its properties.

[0080] In one embodiment of the present disclosure, powder is spread on the etched glass surface rather than through a traditional cladding process that involves precursor material pumped from a nozzle for cladding, but cladding may be utilized in alternative embodiments.

[0081] Mixed powder coatings can have two or more phases of material, i.e., two, three, four, or more different materials. The ratio of mixed powder "1" to powder "2" can also be wide, for example, starting from less than 1% to greater than 99%. Similarly, mixed multi-powder coatings (e.g., a mix of two, three, four, etc.) can have any range of mix percentages, depending on the desired features and material properties.

[0082] Several examples are given in Table 1 and used in the following examples.

[0083] Table 1: Various types of powders used for integrated glass processing using CO2 laser scanning.

[0084] powder Mixed powder Fe Fe+CuCl Mn <![CDATA[TiO2+CuCl]]> Ni <![CDATA[TiO2+Sn]]> Sn <![CDATA[TiO2+BN]]> Zn NaCl+Ni <![CDATA[Fe2O3]]> <![CDATA[TiO2]]> <![CDATA[Ag2O]]> LCO (lithium cobalt oxide) <![CDATA[NaWO4]]> <![CDATA[ZrO2]]> TiN Boron nitride (BN) CuO CuCl CuBr NaCl CoCl BaS <![CDATA[MoS2]]>

[0085] Laser power and scan rate can be tuned within any range of 1W to 30W and 1mm / s to 1000mm / s, which represent the parameters of our laser systems, although parameters outside this range are also permissible. The etch depth can be tuned according to the desired material film thickness with laser power, speed, and multiple scans in the X-axis and Y-axis directions.

[0086] After CO2 laser treatment, the resulting film can have different or similar properties (e.g., electronic, chemical, and mechanical) compared to the original powder. Thus, the choice of powder blend, laser power, and speed enables tuning of electronic properties, morphology, surface area, phase formation, magnetic properties, and more, as required by various applications.

[0087] Although the present disclosure focuses primarily on room temperature (stage temperature) processing under ambient atmospheric conditions, it is not limited to or by these conditions. In addition, the present invention does not exclude the use of organics or mixed systems as co-components such as small molecules, polymers, organic-inorganic hybrids, etc.

[0088] In another embodiment of the present invention, the process can be adapted so that the integrated film on the glass surface produced by the process is functionalized and can be designed to have optimal properties, such as electrical conductivity, surface texture.

[0089] In another embodiment of the present disclosure, the properties of integrated films on glass surfaces, such as electronic, magnetic, chemical, electrochemical, solar, fluorescent, etc., can be tuned through the selection of material powders and their combinations, laser power and scanning speed.

[0090] In another embodiment of the present disclosure, the integrated film on the glass surface cannot be easily removed, such as via ultrasonic treatment or scraping via any complex tool (eg, a doctor blade).

[0091] In another embodiment of the present disclosure, the color and texture of the integrated film can be varied based on the coating material properties and the intensity and nature of the interaction with the glass, which depends on the laser power, speed and characteristics.

[0092] In yet another embodiment of the present disclosure, integrated films on glass via a CO2 laser can be magnetized by the selection of selected precursor powders (eg, Fe).

[0093] In another embodiment of the present disclosure, the integrated film can have different properties from the precursor powder / combined powder and glass via CO2 laser irradiation, such as a different phase formation from the precursor powder material or glass, and the different oxidation state of the film can be different from the oxidation state in the precursor powder due to direct CO2 laser exposure to the precursor powder.

[0094] In one embodiment of the present disclosure, the integrated film can have nanostructured features after exposure to a precursor powder coating on a glass surface. The film thickness can be tuned from nanometers to tens of micrometers.

[0095] In embodiments of the present invention, coating can have the thickness in the nanometer to micrometer range.In some embodiments, coating can have the thickness of at least about 1nm, 5nm, 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, 50nm, 55nm, 60nm, 65nm, 70nm, 75nm, 80nm, 85nm, 90nm, 95nm, 100nm, 150nm, 200nm, 250nm, 300nm, 400nm, 500nm, 600nm or 1000nm.In some embodiments, coating can have the thickness of about 5000nm (5 μm), 10 μm, 15 μm, 20 μm, 25 μm or 50 μm at most. The thickness can range from any of the minimum values recited above to any of the maximum values recited above, such as 1 nm to 20 μm, 500 nm to 20 μm, 1 μm to 20 μm, 2 μm to 20 μm, 5 μm to 20 μm, or 10 μm to 20 μm.

[0096] In one embodiment of the present invention, the integrated membrane comprises "nanoparticles" having sizes in the nanometer range. However, many particles have a wider size range. In some embodiments, the material of step iii) and / or the material or derivative thereof incorporated within the glass substrate in step iv) and / or the material or derivative thereof in the coating on the portion of the surface etched in step iv) may include particles having a z-average diameter of at least about 1 nm, 10 nm, 50 nm, 100 nm, 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1000 nm, 1100 nm, 1200 nm, 1300 nm, 1400 nm, 1500 nm, 1600 nm, 1700 nm, 1800 nm, 1900 nm, 2000 nm, 2500 nm, 3000 nm, 4000 nm, 5000 nm, 6000 nm, 7000 nm, 8000 nm, or at least 9000 nm according to ISO 22412:2017. In some embodiments, the particles may have a z-average diameter of less than 10000 nm, 9000 nm, 8000 nm, 7000 nm, 6000 nm, 5000 nm, 4500 nm, 4000 nm, 3500 nm, 3000 nm, 2500 nm, 2000 nm, 1900 nm, 1800 nm, 1700 nm, 1600 nm, 1500 nm, 1400 nm, 1300 nm, 1200 nm, 1100 nm, 1000 nm, 900 nm, 800 nm, 700 nm, 600 nm, 500 nm, 250 nm, or less than 100 nm according to ISO 22412:2017. The particles may have a z-average diameter according to ISO 22412:2017 ranging from any of the minimum values recited to any of the maximum values recited, for example, 1 nm to 10000 nm, 50 nm to 5000 nm, 100 nm to 2500 nm, 200 nm to 2000 nm, or 500 nm to 1000 nm.

[0097] In yet another embodiment, the present invention may be used in various applications such as energy storage glass, keeping a room warm or cool depending on the materials integrated into the glass, integration of wires and connections, reflection and absorption of specific radiation, magnetism, spintronics, advanced sensors, actuators, and the like.

[0098] Although the foregoing description discloses various embodiments of the present disclosure, other and further embodiments of the present disclosure may be devised without departing from the basic scope of the present disclosure. The invention is not limited to the described embodiments, versions or examples, which are included to enable one skilled in the art to make and use the invention when combined with the information and knowledge available to one skilled in the art.

[0099] Example

[0100] The present invention will be further described below in the form of examples. However, it should be understood that the foregoing examples are merely illustrative and should not be construed as limiting the scope of the present invention. Various changes and modifications to the disclosed embodiments will be apparent to those skilled in the art. Such changes and modifications may be made without departing from the scope of the present invention.

[0101] Reagents and instruments

[0102] Example 1: Functionalization of glass surfaces

[0103] In this example, a glass slide having a size of 7.5 cm×2.5 cm is used, and a grid pattern is formed by etching in a size of 2.5 cm×1.5 cm in the X-axis and Y-axis directions at a predefined laser power and scanning speed.

[0104] In each experiment, the etched surface was coated with a single powder or a combination of powders as needed and spread evenly over the etched surface.

[0105] In the example, the glass slide was initially etched with a CO2 laser along the X-axis and Y-axis directions at a nominal laser power of 6 W and a scan rate of 50 mm / s ( Figure 1B ). Other scan rates and powers are possible.

[0106] A glass slide with powder spread over the etched surface is placed at the focal point of a CO2 laser beam. The powder-coated glass surface is directly irradiated with the CO2 laser. The irradiation power and laser scan rate are tuned within the ranges of 1-30 W and 1 mm / s-1000 mm / s, defining the limits of the laser parameters, but using parameters outside these limits is also possible. More specifically, for the examples presented, 3-6 W laser power and a scan speed of 15 mm-100 mm / s are used in the X-axis direction, but it can be performed in both directions, in other pattern forms, etc., with slightly different effects.

[0107] After irradiation of the powder-coated glass surface, a strongly adherent coating with patterning (direct writing) is obtained as desired. Figure 1C, right part). The slide is then sonicated for 5-15 minutes to remove any residues of the original material and washed in water / solvent, followed by a drying step in a hot air blower or vacuum oven. The resulting film remains firmly bonded to the glass surface even after sonication or scraping.

[0108] Example 2

[0109] Iron (Fe) powder was spread onto the etched glass surface as a coating, and the surface was scanned in the X-axis direction with a laser power of 6 W and a speed of 30 mm / s; this resulted in the Fe particles being integrated into the glass surface. The XRD of the integrated Fe film on the glass is shown below. Figure 2 It was observed that the integrated film had a mixed phase of Fe and Fe3O4. The embedded or integrated coating on glass was found to be highly attracted towards the external magnet from both sides (i.e., opposite and identical faces of the film on glass, as expected for a magnetic coating that is quite strong and thick even on one side). Note that the film was highly uniform and quite flat after treatment, as shown in FESEM analysis ( Figure 3 ) is revealed in.

[0110] Example 3

[0111] Silver oxide powder was coated on an etched glass surface (e.g., 6 W, 50 mm / s, scanning in the X and Y directions) and then irradiated with a CO2 laser directly in the X direction at a scanning speed of 50 mm / s with a laser power of 6 W. It should be noted that the black silver oxide powder was transformed into an orange / light brown integrated film by the CO2 laser treatment. Interestingly, the XRD pattern of the treated coating on the glass ( Figure 4 ) revealed the formation of a silver metallic phase from silver oxide. This implies that the process is essentially reductive in nature. The film was found to be composed of silver nanoparticles and was fully distributed on the glass surface ( Figure 5 ) and inside glass.

[0112] Example 4

[0113] A white anatase TiO2 powder coating was applied to a CO2 laser pretreated glass (pretreated at 6W, 50mm / s, scanning in the X and Y directions). The coated surface was irradiated using a CO2 laser with a power of 4.5-6W and an X-axis scanning speed of 40-60mm / s. The black (suggesting oxygen vacancy defect stabilization) TiO2 rutile phase was found to be integrated into the glass surface, as confirmed by XRD ( Figure 6 ). FESEM analysis revealed that the grown film was highly dense with a uniform and flat (planar) texture ( Figure 7 ).

[0114] Example 5

[0115] A Sn (tin) powder coating was applied to the etched (as described previously) glass surface and scanned in the X-axis direction at a laser power of 6 W and a speed of 50 mm / s. This resulted in a glossy green integrated coating on the glass surface. The coating was found to consist of Sn and SnO2 phases, as confirmed by XRD ( Figure 8 The morphology was found to be highly uniform and flaky ( Figure 9 ). On a smaller scale (right), flake-like morphology appears to be present on the surface. It should be noted here that the film is continuous and conductive on the glass surface, but not very conductive. Post-processing could potentially change the characteristic parameters.

[0116] Example 6

[0117] When the laser was scanned in the X-axis direction with a power of 6W and a scanning speed of 50mm / s, the hematite (α-Fe2O3) powder coating treated by the CO2 laser produced an integrated Fe3O4 ferromagnetic coating. The Fe2O3 powder was red, which was transformed into a black Fe3O4 magnetic film on the surface and inside the glass after CO2 laser treatment. This once again emphasizes the reduction nature of the process, as mentioned previously. Figure 10 ).

[0118] Example 7

[0119] A copper (II) oxide or copper oxide (CuO) powder coating (black) was applied to the etched glass surface and irradiated with a CO2 laser power of 6 W at a scanning rate of 30 / 40 mm / s in the X-axis direction. It was noted that a gold / brown integrated film comprising Cu2O or copper (I) oxide (cuprous oxide) was formed on the glass substrate, further emphasizing the reducing nature of the process. Figure 11 ).

[0120] Various modifications and variations of the assays, techniques, and various means disclosed herein for implementing the assays / methods according to the present invention will be apparent to those skilled in the art without departing from the scope and spirit of the present invention. Although the present invention has been described in conjunction with specific preferred embodiments, it should be understood that the invention as claimed should not be unduly limited to such specific embodiments. Indeed, various modifications of the described modes for carrying out the present invention that are apparent to those skilled in the relevant art are intended to be within the scope of the appended claims.

Claims

1. A process for manufacturing a functionalized glass substrate, the process comprising the following steps in sequence: i) providing a glass substrate, ii) etching the surface of the glass substrate to form an etched surface, iii) contacting at least a portion of the etched surface with a material, iv) laser processing the portion of the etched surface and / or the material to form a functionalized glass substrate, wherein the functionalized glass substrate (a) incorporating the material or its derivative into the glass substrate, and / or (b) comprising a coating of said material or a derivative thereof on said portion of said etched surface.

2. The process according to claim 1, wherein The etching of the surface of the glass substrate in step ii) is performed by laser processing and / or chemical processing, preferably by laser processing.

3. A process according to any preceding claim, wherein The laser treatment of step iv) and / or the laser treatment of step ii) when present is performed using a gas laser selected from a xenon ion laser, a nitrogen laser, a krypton laser, a helium-neon laser, an excimer laser, a carbon monoxide laser, a carbon dioxide laser and / or an argon laser, preferably using a carbon dioxide laser.

4. A process according to any preceding claim, wherein The laser treatment of step iv) and / or the laser treatment of step ii) when present is performed using a laser power of 1 to 50 W, preferably 1 to 40 W, more preferably 1 to 30 W.

5. A process according to any preceding claim, wherein The laser treatment of step iv) and / or the laser treatment of step ii) when present is performed using a laser scanning speed of 1 mm / s to 10000 mm / s, preferably 1 mm / s to 5000 mm / s, more preferably 1 mm / s to 1000 mm / s, most preferably 10 mm / s to 500 mm / s.

6. A process according to any preceding claim, wherein The laser treatment of step iv) and / or the laser treatment of step ii) when present is performed using a carbon dioxide laser emitting at 9-11 μm, preferably 10.6 μm.

7. A process according to any preceding claim, wherein The laser treatment of step iv) and / or the laser treatment of step ii) when present is performed in continuous wave, pulsed and / or scanned mode.

8. A process according to any preceding claim, wherein The laser treatment of step iv) and / or the laser treatment of step ii) when present is performed in an air atmosphere or an inert atmosphere.

9. The process according to any one of claims 2 to 8, wherein When present, the chemical treatment of step ii) is performed using hexafluorosilicic acid, hydrogen fluoride, hydrofluoric acid, sodium fluoride and / or ferric chloride.

10. A process according to any preceding claim, wherein The material of step iii) is in the form of a solid, preferably a powder.

11. A process according to any preceding claim, wherein The material of step iii), and / or the material or derivatives thereof incorporated into the glass substrate in step iv), and / or the material of the coating on the portion of the etched surface in step iv), or derivatives thereof, comprises particles having a z-average diameter according to ISO 22412:2017 of 1 nm to 10,000 nm, preferably 50 nm to 5,000 nm, more preferably 100 nm to 2,500 nm, even more preferably 200 nm to 2,000 nm, most preferably 500 nm to 1,000 nm.

12. A process according to any preceding claim, wherein The material of step iii), and / or the material incorporated into the glass substrate in step iv), or a derivative thereof, and / or the material of the coating on the portion of the etched surface in step iv), or a derivative thereof, comprises one or more metals, metal oxides, nitrides, sulfides, and / or halides, such as chlorides or bromides.

13. A process according to any preceding claim, wherein The material of step iii) and / or the material incorporated into the glass substrate in step iv) or a derivative thereof and / or the material of the coating on the portion of the etched surface in step iv) or a derivative thereof include one or more of Fe, Mn, Ni, Sn, Zn, Fe2O3, TiO2, Ag2O, LCO (lithium cobalt), NaWO4, ZrO2, TiN, BN, CuO, CuCl, CuBr, NaCl, CoCl, BaS and / or MoS2.

14. A process according to any preceding claim, wherein When present, the material or its derivatives incorporated within the glass substrate are up to 50 μm from the etched surface, preferably up to 25 μm from the etched surface, more preferably up to 20 μm from the etched surface, and most preferably up to 20 μm to up to 10 μm from the etched surface when viewed perpendicular to the etched surface of the glass substrate.

15. A process according to any preceding claim, wherein When present, the material or derivatives thereof incorporated within the glass substrate forms a gradient in its frequency when moving perpendicularly from the etched surface.

16. A process according to any preceding claim, wherein Step iv) further comprises performing ultrasonic treatment on the functionalized glass substrate, and preferably, drying the functionalized glass substrate after performing ultrasonic treatment on the functionalized glass substrate.

17. Use of a functionalized glass substrate produced according to the process of any preceding claim in an architectural, automotive or electronic application, such as a glass frame, a wall, a partition, a shutter, a door, an electronic device such as a PV module, a liquid crystal display or an OLED, a touch screen, a mirror, a container, furniture, a splashback, a car window, an energy storage glass, an electrical connector, a sensor, an actuator, a magnetic device and / or a spintronic device.

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