Integrated patterning and functionalization process for glass coatings and uses thereof - Patents.com

Abstract

The present disclosure relates to a process for functionalizing glass. Specifically, it is a process for producing patterned functional coatings on glass surfaces. In particular, the present disclosure provides a process for integrating an integral, embedded, inseparable functionalized powder coating onto a glass surface by patterned line-scan irradiation of a CO2 laser. The present invention also relates to the use of said functionalized glasses 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 that can be utilized to integrate an integral, embedded, inseparable functionalized powder coating onto a glass surface by patterned line-scan irradiation of a CO2 laser. The invention also relates to the use of said functionalized glass substrates in a variety of applications such as energy storage glass, keeping rooms warm or cold depending on the materials integrated into the glass, integration of electrical wiring and connections, reflection and absorption of specific radiation, magnetics, spintronics, advanced sensors, actuators, etc. [Background technology]

[0002] The background discussion 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 of the publications specifically or implicitly referenced are prior art.

[0003] Glass is traditionally a building material or a passive support material in some technical applications. Glass may be functionalized by doping with specific elements during its formation. Laser engraving of glass is also done using lasers of different wavelengths and for different applications.

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

[0005] Indeed, the incorporation and reactive integration of such materials onto the surface layer of glass can produce entirely new materials and phases with previously unrealized compositions, structures and properties.

[0006] This has the potential to dramatically broaden and enhance the applicability of prefabricated glasses, otherwise used as passive support materials, into application domains such as energy, magnetics, spintronics, advanced sensors, and actuators.

[0007] Thus, herein we disclose the development of a process that allows for the extension of the application range of glass through synergistic incorporation and reactive integration with other functional materials, particularly their powder forms. [Object of the Invention]

[0008] It is an object of the present invention to provide a process for functionalizing glass substrates.

[0009] It is an object of the present invention to provide a process for producing patterned functional coatings on glass surfaces.

[0010] Another object of the present invention is to provide a process for integrating an integral, embedded, non-detachable functionalized powder coating onto a glass surface by patterned line-scan irradiation of a CO2 laser.

[0011] It is yet another object of the present invention to provide glass functionalized by the processes disclosed herein for a variety of applications. Summary of the Invention

[0012] This Summary is provided to introduce a selection of concepts in a simplified form that are further described below in the Detailed Description section. 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.

[0013] In one aspect, 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 etching surface with a material; iv) laser processing the portion of the etched surface and / or the material to form a functionalized glass substrate, the functionalized glass substrate comprising: (a) the material or a derivative thereof is incorporated into the glass substrate; and / or (b) step iv) comprising coating said portion of said etched surface with said material or a derivative thereof.

[0014] Surprisingly, it has been established that the process of the present invention can result in the incorporation and reactive integration of materials into glass substrates.

[0015] Etching the surface of the glass substrate in step ii) may be performed by laser processing and / or chemical treatment, preferably by laser processing.

[0016] When present, the laser processing in step ii) may 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, if present, said laser processing in 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, said laser processing in step ii) is performed using a carbon dioxide laser. The carbon dioxide laser preferably emits light at 9 to 11 μm, more preferably at 10.6 μm.

[0017] If present, the laser processing in step ii) may be carried out using a laser power of 1-50W, more preferably 1-40W, even more preferably 1-30W. If present, the laser processing in step ii) may be performed at 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 processing may be performed in continuous wave, pulsed, scanned, or any other suitable mode.

[0018] The laser processing in step iv) may 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 processing 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, said laser processing in step iv) is performed using a carbon dioxide laser. The carbon dioxide laser preferably emits light at 9 to 11 μm, more preferably at 10.6 μm.

[0019] The laser processing in step iv) may be carried out using a laser power of 1-50W, more preferably 1-40W, and even more preferably 1-30W. The laser processing in step iv) may be performed at 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 processing may be performed in continuous wave, pulsed, scanned, or any other suitable mode.

[0020] When present, the chemical treatment in step ii) may be carried out using hexafluorosilicic acid, hydrogen fluoride, hydrofluoric acid, sodium fluoride, and / or ferric chloride.

[0021] 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 a grid.

[0022] Preferably, said material in step iii) is in the form of a solid, more preferably a powder, or a film adhered to said portion of said etched surface. If the material in step iii) is in the form of a film adhered to the portion of the etched surface, preferably the film is 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 by other suitable methods such as chemical vapor deposition, plating, sputtering, or evaporation techniques.

[0023] The material in step iii) and / or the material or derivatives thereof incorporated into the glass substrate in step iv) and / or the material or derivatives thereof of the coating on the portion of the etched surface in step iv) may comprise 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 in accordance with ISO 22412:2017. In some embodiments, the particles may have a z-average diameter of less than 10,000 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 may range from any of the minimum values ​​above to any of the maximum values ​​above, for example, from 1 nm to 10,000 nm, from 50 nm to 5,000 nm, from 100 nm to 2500 nm, from 200 nm to 2000 nm, or from 500 nm to 1000 nm.

[0024] The material in step iii) and / or the material or derivatives thereof incorporated into the glass substrate in step iv) and / or the material or derivatives thereof of the coating on the portion of the etched surface in step iv) may comprise an inorganic material, a polymer, an organic molecule, an organic-inorganic hybrid material, etc., or any combination thereof. Preferably, the material comprises one or more metals, metal oxides, nitrides (e.g., TiN, BN, etc.), sulfides (e.g., MOS2, BaS, etc.), and / or halides, such as chlorides (NaCl, CuCl, CoCl, etc.) or bromides (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 comprise a mixture of materials, for example the material may comprise Fe and CuCl, or TiO2 and CuCl, or TiO2 and Sn, or TiO2 and BN, or NaCl and Ni. The materials may be combinations of metals, oxides, nitrides, sulfides, etc., and may include a wide range of other classes (e.g., superconducting materials, thermoelectric materials, polymeric materials, etc.) without being limited to those mentioned above.

[0025] Preferably, said material in step iii) is provided as a layer on said 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 etching surface. In some embodiments, the layer may be provided in distinct regions of the etching surface, for example in the areas where etching has occurred. Preferably, the layer of material on the etched surface has a thickness of 10 μm to 100 μm, more preferably 1 nm to 10 μm.

[0026] When viewed perpendicularly to the etched surface of the glass substrate, the material or derivative thereof incorporated into the glass substrate is preferably located at a distance of 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 10 μm from the etched surface. The material or derivative thereof incorporated into the glass substrate may form a gradient with respect to its frequency when moving perpendicular to the etching surface from the etching surface.

[0027] The laser processing in step iv) can result in a reduction of material.

[0028] The process may be carried out in an air atmosphere or an inert atmosphere.

[0029] Preferably, step iv) further comprises ultrasonic treatment of said functionalized glass substrate. The sonication may be carried out in a suitable organic or aqueous solvent. Preferably, following ultrasonic treatment of the functionalized glass substrate, the functionalized glass substrate is dried, preferably using a hot air blower or an oven.

[0030] In one embodiment, the present disclosure relates to a process for functionalizing a glass substrate surface effected by a CO2 laser (10.6 μm wavelength) based direct-write patternable transient photothermal process in scanning mode (x, y, or x and y) to integrally and reactively incorporate a powder coated layer onto the surface of the glass.

[0031] In one embodiment of the present disclosure, the powder is spread onto the etched glass surface rather than by a conventional cladding process that pumps precursor material through a nozzle for cladding.

[0032] In one embodiment of the present disclosure, the solution provided by the present invention takes the form of treating a glass surface coated with one or more functional materials with a scanned CO laser beam, whereby the transient heat pulse delivered by the scanned laser beam results in the incorporation and reactive integration of both the materials and the glass surface.

[0033] In yet another embodiment of the present disclosure, the derivative of the functionalized glass substrate may have different properties (eg, electronic, chemical, and mechanical) compared to the material.

[0034] Preferably, the surface of the glass substrate is a main surface of the glass substrate. Preferably, the glass substrate is transparent. The glass substrate may 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 with an Fe2O3 content of less than about 0.05% by weight is typically referred to as low-iron float glass. Such glasses typically have the same basic composition with the other constituent oxides, i.e., low iron float glass is a soda lime silicate glass, as is clear float glass. Typically, low iron float glass has less than 0.02 wt. % Fe2O3. Alternatively, the glass pane is a borosilicate-based glass pane, an alkali aluminosilicate-based glass pane, or an aluminum oxide-based crystallized glass pane.

[0035] According to a second aspect of the present invention there is provided the use of a functionalised glass substrate produced by the process of the first aspect in architectural, automotive or electronic applications, for example glazing, walls, bulkheads, blinds, doors, PV modules, electronic devices such as liquid crystal displays or OLEDs, touch screens, mirrors, containers, furniture, splashbacks, vehicle windows, energy storage glass, electrical connectors, sensors, actuators, magnetics and / or spintronics.

[0036] Various objects, features, aspects and advantages of the present subject matter will become more apparent from the following detailed description of preferred embodiments. [Brief explanation of the drawings]

[0037] The features and advantages of the subject matter disclosed in this disclosure will become more apparent from the detailed description of the embodiments, given by way of example only, with reference to the accompanying drawings, in which:

[0038] [Figure 1A] 1 is a flow chart of a process according to the present invention.

[0039] [Figure 1B] A glass substrate etched along the x and y directions by line scanning of a CO2 laser. [Figure 1C] 1 is an in-plane interfacial area (top or surface view) of an etched glass substrate and an integral film.

[0040] [Figure 2] XRD of the integrally fused Fe powder coating on the glass surface.

[0041] [Figure 3] FE-SEM images of embedded or integrally functionalized Fe powder coatings after CO2 laser irradiation.

[0042] [Figure 4]XRD of a silver oxide powder coating on a glass surface treated with a CO2 laser. The powder was converted into a nanosilver film.

[0043] [Figure 5] FESEM morphology: Nanosilver film from Ag2O powder on glass.

[0044] [Figure 6] XRD analysis reveals that the starting material anatase TiO2 is used to form films of oxygen vacancy defects-rutile (black) phase.

[0045] [Figure 7] FESEM image of a rutile TiO2 film on a glass surface.

[0046] [Figure 8] 1 is an XRD of a laser treated Sn powder coating showing the formation of a mixed phase of Sn and SnO2.

[0047] [Figure 9] FESEM analysis reveals that CO2 laser treatment uses Sn powder to form a continuous and dense film of Sn and SnO2.

[0048] [Figure 10] XRD of a black FC3O4 film that was integrated into the glass surface by CO2 laser treatment of hematite (Fe2O3) coated glass.

[0049] [Figure 11] XRD of a copper(I) oxide (CuO) coating produced on glass using a copper(II) oxide (CuO) powder coating by CO laser treatment. DETAILED DESCRIPTION OF THE INVENTION

[0050] The following is a detailed description of embodiments of the present disclosure. The embodiments are in sufficient detail to clearly communicate the present disclosure. However, the degree of detail provided is not intended to limit the possible variations of the embodiments, but rather to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the present disclosure as defined by the appended claims.

[0051] 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. If a definition or use of a term in an incorporated reference contradicts or is 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.

[0052] References throughout this specification to "one embodiment" or "an embodiment" mean that a particular feature, structure, or characteristic described in connection with this embodiment is included in at least one embodiment. Thus, the appearances of the phrases "in one embodiment" or "in an embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.

[0053] In some embodiments, numbers are used to quantify weight percentages, degrees, and the like to describe and claim particular embodiments of the present invention, and these should be understood as being modified in some cases by the term "about." Accordingly, in some embodiments, the numerical parameters set forth in the specification and appended claims are approximations that may vary depending upon the desired properties sought to be obtained by a particular embodiment. In some embodiments, the numerical parameters should be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of some embodiments of the invention are approximations, the numerical values ​​set forth in the specific examples are reported as precisely as practicable. The numerical values ​​presented in some embodiments of the invention may contain certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

[0054] Various terms used herein are set forth below. Unless a term used in the claims is defined below, it should be given the broadest definition that one of ordinary skill in the art could give that term, as reflected in the printed publications and issued patents at the time of filing.

[0055] As used throughout this description and the claims that follow, the meanings of "a," "an," and "the" include plural references unless the context clearly dictates otherwise. Also, as used in this description, the meaning of "in" includes "in" and "on" unless the context clearly dictates otherwise.

[0056] Unless the context requires otherwise, throughout the following specification, the word "comprise" and variations thereof, such as "comprises" and "comprising," are to be interpreted in their open and inclusive sense of "including, but not limited to."

[0057] Recitation of ranges of values ​​herein is merely intended to serve as a shorthand method of referring individually to each separate value falling within the range. Unless otherwise indicated herein, each individual value is incorporated herein as if individually set forth herein. In the discussion of the invention herein, unless stated to the contrary, the disclosure of alternative values ​​for the upper or lower limits of an acceptable range of a parameter, coupled with an indication that one of said values ​​is significantly more preferred than the other, should be construed as an implicit statement that each intermediate value of said parameter between the more preferred and less preferred of said alternative values ​​is itself preferable to said less preferred value and each value between said less preferred value and said intermediate value.

[0058] All methods described herein may be performed in any suitable order unless otherwise indicated herein or clearly contradicted by context. Any and all examples provided with respect to specific embodiments herein, or the use of exemplary language (e.g., "etc."), are intended merely to better describe the invention and do not otherwise limit the scope of the invention as claimed. No language in the specification should be construed as indicating any non-claimed element essential to the practice of the invention.

[0059] Groupings of alternative elements or embodiments of the invention disclosed herein are not to be construed as limitations. Each group member may be referenced and claimed individually or in any combination with other members of the group or other elements found herein. One or more members of a group may be included in, or deleted from, a group for reasons of convenience and / or patentability. When any such inclusion or deletion occurs, the specification is deemed to include the modified group.

[0060] The following description, and the embodiments described therein, are provided as illustrations of one or more examples of particular embodiments of the principles and aspects of the present disclosure. These examples are offered by way of illustration of these principles and of the present disclosure, and not by way of limitation.

[0061] The headings and abstracts of the invention provided herein are for convenience only and do not interpret the scope or meaning of the embodiments.

[0062] The following description provides a number of exemplary embodiments of the present subject matter. Although each embodiment represents a single combination of elements of the invention, it is contemplated that the inventive subject matter includes all possible combinations of the disclosed elements. Thus, if one embodiment includes elements A, B, and C, and a second embodiment includes elements B and D, it is believed that the inventive subject matter also includes other remaining combinations of A, B, C, or D, even if not explicitly disclosed.

[0063] Various terms are used herein. Unless a term used in the claims is defined below, it should be given the broadest definition that one of ordinary skill in the art could give that term, as reflected in the printed publications and issued patents at the time of filing.

[0064] In the context of this invention, a "derivative" is a chemical substance that is structurally related to and theoretically derivable from another chemical substance.

[0065] In the context of the present invention, the "thickness" of a layer is represented, for any given position on the surface of the layer, by the distance through the layer in the direction of the smallest dimension of the layer from said position on the surface of the layer to a position on the opposite surface of the layer.

[0066] While particular forms of the invention have been illustrated and described, it will be apparent that various modifications can be made without departing from the spirit and scope of the invention.

[0067] Embodiments of the present disclosure relate to a process for producing a patterned functional coating on a glass layer. In particular, the present disclosure provides a process for integrating an integral, embedded, inseparable functionalized powder coating onto a glass surface by patterned line-scan irradiation of a CO2 laser. The present invention also relates to the use of the functionalized glass in various applications.

[0068] In one embodiment, the solution provided by the present disclosure takes the form of treating a glass surface coated with one or more functional materials with a scanned CO laser beam, whereby the transient heat pulse delivered by the scanned laser beam results in the incorporation and reactive integration of both the materials and the glass surface. This method simultaneously heats both the glass surface and the coated powder material to allow and promote rapid diffusional incorporation of species and reactions between species. The "built-in" portion further distinguishes the present invention from commonly used surface coating methods in which the glass and coating maintain their own identity and properties.

[0069] In one embodiment of the present disclosure, the functionalization is provided by a CO2 laser (10.6 μm wavelength) based direct-write patternable transient photothermal process in scanning mode (x, y, or x and y) to integrally and reactively incorporate a powder coated layer onto the surface of the glass.

[0070] In one embodiment of the present disclosure, the CO2 laser power and scanning speed may be in the ranges of 1 W to 30 W and 1 mm / s to 1000 mm / s, respectively, but are not limited to these ranges.

[0071] According to this embodiment, various types of material powders, such as metal, metal oxide, nitride, carbide, chloride, sulfide, etc. powders, can be used to achieve integrally and / or reactively bonded uniform or patterned coatings on the glass surface. Furthermore, mixed powders of metals and metal oxides, chlorides, nitrides, sulfides, etc. can also be integrated onto the glass surface, potentially resulting in engineered compound or composite layers on the surface. The powder combinations can be varied widely, for example, mixing metal / semi-metal oxides, oxides with other oxides, metals with other metals, oxides with nitrides or chlorides, and the like. The thickness of the material (layer of material) used as a coating prior to laser processing dictates the laser energy density and scanning speed to achieve the desired property set and gradient of material composition as a function of depth.

[0072] As mentioned above, the process according to the present invention is shown as a flow chart in FIG. 1A and consists of patterned etching of the glass surface with a CO laser, followed by uniformly spreading the desired precursor powder coating and irradiating the coated surface with the laser (no medium other than air / ambient) in line scan mode in single or multiple scan modes in the x and / or y directions, with or without scan or partial scan overlap, under normal atmospheric conditions. The process may further include a step of sonicating the functionalized glass in a suitable solvent / water, followed by a drying step using a hot air blower / oven. The precursor powder is selected from materials that are metal / metal oxides, nitrides, sulfides, chlorides, and / or combinations thereof. The use of a CO2 laser in scanning mode is important because it provides transient heating at any local spot and the laser itself can be operated in CW or pulsed mode, leading to different results in terms of the final material obtained and its properties.

[0073] In one embodiment of the present disclosure, the powder is spread onto the etched glass surface rather than by a traditional cladding process that pumps precursor material through a nozzle for cladding, although cladding can be utilized in alternative embodiments.

[0074] The mixed powder coating can be a two-phase or multi-phase material, ie, have two, three, four, or more different materials. The mixing ratio of powder "1" to powder "2" may be broad, for example, from less than 1% to more than 99%. Similarly, mixed coatings of multiple powders (eg, two, three, four, etc. mixes) can have any range of mix percentages depending on the desired characteristics and material properties.

[0075] Some examples are shown in Table 1 and are used in the following examples.

[0076] Table 1. Different types of powders used in integral glass processing using CO2 laser scanning [Table 1]

[0077] The laser power and scanning speed can be adjusted to any range between 1 W and 30 W and 1 mm / s and 1000 mm / s, which represent the parameters of the laser system of the present invention, although parameters outside these ranges are also possible. The etch depth can be adjusted by laser power, speed, and number of scans in the X and Y axes depending on the desired thickness of the material film.

[0078] After CO2 laser treatment, the formed film can have different or similar properties (e.g., electronic, chemical, and mechanical) compared to the original powder. Thus, powder mixing, laser power selection, and speed allow tuning of electronic properties, morphology, surface area, and phase formation, variations in magnetic properties, and many more variations depending on the requirements of different applications.

[0079] This disclosure focuses primarily on room temperature (stage temperature) processing under ambient atmospheric conditions, but is not limited to or by these conditions. Also, the present invention does not exclude the use as co-components of organic or hybrid systems such as small molecules, polymers, organic-inorganic hybrids, etc.

[0080] In another embodiment of the present disclosure, a process can be employed such that the integral film on the glass surface produced by the described process can be functionalized and designed to have optimal properties such as conductivity, surface texture, etc.

[0081] In another embodiment of the present disclosure, the electronic, magnetic, chemical, electrochemical, solar, fluorescent, etc. properties of the integral film on the glass surface can be tailored by the selection of material powders and their combinations, laser power, and scanning speed.

[0082] In another embodiment of the present disclosure, the integral film on the glass surface cannot be easily removed, for example, by sonication or scratching with any complex tool (e.g., a spatula).

[0083] In another embodiment of the present disclosure, the color and texture of the integral film can change depending on the laser power, speed, and properties, depending on the properties of the coating material and the strength and nature of its interaction with the glass.

[0084] In yet another embodiment of the present disclosure, CO2 laser monolithic films on glass can be magnetized by a selection of selected precursor powders (e.g., Fe).

[0085] In yet another embodiment of the present disclosure, the monolithic film can have different properties from the precursor powder / combination powder and glass due to the CO2 laser irradiation, for example, different phase formation from the precursor powder material or glass, and the different oxidation state of the film can be different from that in the precursor powder due to the direct CO2 laser exposure to the precursor powder.

[0086] In one embodiment of the present disclosure, the monolithic film can have nano-structural features after CO2 laser exposure to the precursor powder coating on the glass surface. The film thickness can be adjusted from nanometers to tens of micrometers.

[0087] In one embodiment of the present invention, the coating can have a thickness ranging from nanometers to micrometers. In some embodiments, the coating may have a thickness of at least about 1 nm, 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm, 55 nm, 60 nm, 65 nm, 70 nm, 75 nm, 80 nm, 85 nm, 90 nm, 95 nm, 100 nm, 150 nm, 200 nm, 250 nm, 300 nm, 400 nm, 500 nm, 600 nm, or 1000 nm. In some embodiments, the coating may have a thickness of up to about 5000 nm (5 μm), 10 μm, 15 μm, 20 μm, 25 μm, or 50 μm. The thickness may range from any of the above minimum values ​​to any of the above maximum values, for example, from 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.

[0088] In an embodiment of the present invention, the monolithic film comprises "nanoparticles" having sizes on the nanometer scale. However, many particles have a wider range of sizes. In some embodiments, the material in step iii) and / or the material or derivatives thereof incorporated into the glass substrate in step iv) and / or the material or derivatives thereof of the coating on the portion of the etched surface in step iv) may comprise 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 in accordance with ISO 22412:2017. In some embodiments, the particles may have a z-average diameter of less than 10,000 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 ​​listed above to any of the maximum values ​​listed above, for example, from 1 nm to 10,000 nm, from 50 nm to 5,000 nm, from 100 nm to 2500 nm, from 200 nm to 2000 nm, or from 500 nm to 1000 nm.

[0089] In yet another embodiment, the present invention can be used in a variety of applications such as energy storage glass, keeping rooms warm or cold depending on the materials integrated into the glass, integration of electrical wiring and connections, reflection and absorption of specific radiation, magnetics, spintronics, advanced sensors, actuators, etc.

[0090] While the forgoing disclosure discloses various embodiments of the present disclosure, other and further embodiments of the present invention may be devised without departing from the basic scope thereof. The present invention is not limited to the described embodiments, versions, or examples that are included to enable those skilled in the art to make and use the invention when combined with information and knowledge available to those skilled in the art. [Example]

[0091] The present disclosure is further illustrated in the form of the following examples. However, it should be understood that the foregoing examples are merely illustrative and should not be construed as limitations on 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 can be made without departing from the scope of the present invention. [Reagents and equipment]

[0092] Example 1: Functionalization of glass surfaces A glass slide having dimensions of 7.5 cm x 2.5 cm was used in the examples and was etched in the X and Y directions over a dimension of 2.5 cm x 1.5 cm at a given laser power and scan speed to form a grid pattern. In each experiment, the etched surface was coated with a single powder or a combination of powders, spread evenly over the etched surface as needed. In the example, a glass slide was first etched along the X and Y axes with a CO 2 laser at a nominal laser power of 6 W and a scanning speed of 50 mm / s (FIG. 1B). Other scan rates and outputs are possible. The glass slide with the powder spread on the etched surface was placed at the focus of the CO2 laser beam. The CO2 laser was directly irradiated onto the powder-coated glass surface. The irradiation power and laser scanning speed were adjusted in the ranges of 1 to 30 W and 1 mm / s to 1000 mm / s, which define the parameter limits of the laser, but the use of parameters outside these limits is also feasible. More specifically, in the examples presented, a laser power of 3 to 6 W and a scanning speed of 15 to 100 mm / s were used in the X-axis direction, but other pattern shapes can also be used in both directions, with slightly different effects. After irradiation of the powder-coated glass surface, a strong, adherent coating was obtained, which was patterned (direct-written) as desired ( Figure 1C , right part). The glass slides were then subjected to ultrasonic treatment to remove any residues of pure material ranging from 5 to 15 min, washed in water / solvent, followed by a drying step in a hot air blower or vacuum oven. The resulting film remained strong and intact to the glass surface, even after sonicating or scratching the film.

[0093] Example 2 Iron (Fe) powder was spread as a coating on the etched glass surface, and the surface was scanned in the X-axis direction with a laser power of 6 W and a speed of 30 mm / s, resulting in the integration of Fe particles into the glass surface. The XRD of the monolithic Fe film on glass is shown in Figure 2 below. The monolithic film is observed to have a mixed phase of Fe and Fe3O4. It was found that the embedded or integral coating on the glass was strongly attracted towards the external magnet from both sides (i.e., the same side opposite the film on the glass), as would be expected for a fairly strong and fairly thick magnetic coating even on one side. It is noted that the post-treatment of the film is very uniform and fairly flat, as evident in the FESEM analysis (Figure 3).

[0094] Example 3 Silver oxide powder was coated onto the etched glass surface (e.g., 6 W, 50 mm / s, scanning in the X-axis and Y-axis directions), and then directly irradiated with a CO2 laser at a scanning speed of 50 mm / s and a laser power of 6 W in the X-axis direction. Note that the black silver oxide powder was transformed into an orange / light brown monolithic film by CO2 laser treatment. Interestingly, XRD of the treated coating on glass (Figure 4) revealed the formation of a silver metal phase from silver oxide. This means that the process is reductive in nature. The film consists of nanosilver particles, which can be seen to be completely distributed over the entire glass surface (Figure 5) and also within the glass.

[0095] Example 4 A white anatase TiO2 powder coating was applied onto the pretreated glass with a CO2 laser (6 W, pretreatment at 50 mm / s, scanning in X and Y directions). A CO2 laser with a power of 4.5-6 W and an X-axis scanning speed of 40-60 mm / s was used to irradiate the coated surface. A black (indicating oxygen vacancy-stabilized) TiO2 rutile phase was found to be integrated into the glass surface, as confirmed by XRD (Figure 6). FESEM analysis reveals that the grown films are dense and have a uniform, flat (planar) texture (Figure 7).

[0096] Example 5 A Sn(Tin) powder coating was applied onto the etched glass surface (as described above) and scanned in the X-axis direction with a laser power of 6 W and a speed of 50 mm / s. This resulted in a glossy, green, integral coating on the glass surface. The coating was found to be composed of Sn and SnO2 phases as confirmed by XRD (Fig. 8). The morphology was found to be very uniform and sheet-like (Figure 9). At a smaller scale (right), a sheet-type morphology appears to be present on the surface. Note that the film is continuous on the glass surface and is conductive, but not very conductive. Post-processing can change the characteristic parameters.

[0097] Example 6 Hematite (alpha-Fe2O3) powder coatings treated with a CO2 laser give an integral Fe3O4 ferromagnetic coating when scanned in the X-axis direction with the laser having a power of 6 W and a scanning speed of 50 mm / s. The Fe2O3 powder has a red color that is transformed by CO2 laser treatment into a black Fe3O4 magnetic film on the surface of the glass and also within the glass. This again, as previously mentioned, emphasizes the reduction properties of the process. (Figure 10).

[0098] Example 7 Copper (II) oxide or cupric oxide (CuO) powder coating (black) was applied onto the etched glass surface and irradiated with a CO2 laser with a scanning speed of 30 / 40 mm / s and an irradiation power of 6 W in the X-axis direction. A gold / brown monolithic film containing Cu2O or copper(I) oxide (cuprous oxide) was observed to form on the glass substrate, further highlighting the reducing nature of the process. (Figure 11).

[0099] Various modifications and variations of the described assays, techniques, and various means for carrying out the assays / methods of the present invention disclosed herein will be apparent to those skilled in the art without departing from the scope and spirit of the invention. Although the invention has been described in connection 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 invention which are obvious to those skilled in the relevant fields are intended to be within the scope of the following claims.

Claims

1. i) providing a glass substrate; ii) etching a surface of the glass substrate to form an etched surface; iii) contacting at least a portion of the etching surface with a material; iv) laser processing the portion of the etched surface and / or the material to form a functionalized glass substrate, the functionalized glass substrate comprising: (a) the material or a derivative thereof is incorporated into the glass substrate; and / or (b) step iv) comprising coating said portion of said etched surface with said material or a derivative thereof.

2. 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 treatment, preferably by laser processing.

3. 3. The process according to claim 1 or 2, wherein the laser processing in step iv) and / or, if present, the laser processing in step ii) is carried out 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 a carbon dioxide laser.

4. 4. The process according to any one of claims 1 to 3, wherein the laser processing in step iv) and / or, if present, in step ii) is carried out using a laser power of 1 to 50 W, preferably 1 to 40 W, more preferably 1 to 30 W.

5. 5. The process according to any one of claims 1 to 4, wherein the laser processing in step iv) and / or, if present, in step ii) is performed at 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. 6. The process according to any one of claims 1 to 5, wherein the laser processing in step iv) and / or, if present, in step ii) is carried out using a carbon dioxide laser emitting at 9-11 μm, preferably 10.6 μm.

7. The process according to any one of claims 1 to 6, wherein the laser processing in step iv) and / or, if present, in step ii) is performed in continuous wave, pulsed and / or scanning mode.

8. The process according to any one of claims 1 to 7, wherein the laser processing in step iv) and / or, if present, in step ii) is carried out in an air atmosphere or an inert atmosphere.

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

10. The process according to any one of claims 1 to 9, wherein the material in step iii) is in the form of a solid, preferably a powder.

11. 11. The process according to any one of the preceding claims, wherein the material in step iii) and / or a material or derivative thereof incorporated into the glass substrate in step iv) and / or a material or derivative thereof of the coating on the part of the etched surface in step iv) 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 2500 nm, even more preferably 200 nm to 2000 nm and most preferably 500 nm to 1000 nm.

12. 12. The process according to any one of claims 1 to 11, wherein the material in step iii) and / or the material or derivatives thereof incorporated into the glass substrate in step iv) and / or the material or derivatives thereof of the coating on the part of the etched surface in step iv) comprises one or more metals, metal oxides, nitrides, sulfides and / or halides, such as chlorides or bromides.

13. The material in step iii) and / or the material or derivative thereof incorporated in the glass substrate in step iv) and / or the material or derivative thereof of the coating on the part of the etched surface in step iv) may be Fe, Mn, Ni, Sn, Zn, Fe ２ O ３ , TiO, Ag ２ O, LCO (lithium cobalt oxide), NaWO ４ , ZrO ２ , TiN, BN, CuO, CuCl, CuBr, NaCl, CoCl, BaS, and / or MoS ２ The process according to any one of claims 1 to 12, comprising one or more of:

14. 14. The process of any one of claims 1 to 13, wherein the material or derivative thereof incorporated into the glass substrate, when present, is located at a distance of up to 50 μm from the etched surface of the glass substrate, preferably at a distance of up to 25 μm from the etched surface, more preferably at a distance of up to 20 μm from the etched surface, and most preferably at a distance of up to 20 μm to a distance of up to 10 μm from the etched surface when viewed perpendicular to the etched surface of the glass substrate.

15. 15. The process of any one of claims 1 to 14, wherein the material or derivative thereof incorporated into the glass substrate, if present, forms a gradient with respect to its frequency when moving perpendicular to the etched surface from the etched surface.

16. 16. The process according to any one of claims 1 to 15, wherein step iv) further comprises ultrasonic treatment of the functionalized glass substrate, preferably wherein ultrasonic treatment of the functionalized glass substrate is followed by drying the functionalized glass substrate.

17. 17. Use of a functionalized glass substrate produced by the process of any one of claims 1 to 16 in architectural, automotive or electronic applications, for example framing for glazing, walls, bulkheads, blinds, doors, PV modules, electronic devices such as LCDs or OLEDs, touch screens, mirrors, containers, furniture, splashbacks, vehicle windows, energy storage glass, electrical connectors, sensors, actuators, magnetics and / or spintronics.

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