METHOD FOR PREPARING COATINGS TO IMPROVE THE STRENGTH AND FRACTURE TOUGHNESS OF GLASS, AND COATING PREPARED BY SAID METHOD

Abstract

The present invention relates to a coating and a preparation thereof for improving the strength and fracture toughness of glass, comprising the hydrolytic polycondensation product of one or more alkaxisilane(s) with one or more metal oxide(s) and / or metal alkoxide(s) in the presence of water and a catalyst. The present invention also relates to the use of the coating for repairing damaged silica-containing materials.

Description

The present invention relates generally to methods and systems for improving the strength and fracture toughness of glass or for repairing damaged glass or any silica-containing material. In particular, the present invention relates to the use of a coating for these purposes comprising the hydrolytic polycondensation product of one or more alkoxysilane(s) with one or more metal or metalloid oxide(s) and / or metal or metalloid alkoxide(s) in the presence of water and a catalyst. BACKGROUND The strength of glass drops drastically after exposure to atmospheric humidity (for example, in moderate climates up to 77 ppm (0.1 g / Nm³, equivalent to 20% relative humidity at -30°C) in extremely cold and dry winter weather and up to 90,000 ppm (115 g / Nm³, equivalent to 100% humidity at +60°C) in extremely humid summer weather) and high forming temperatures where water or hydroxyl groups are chemically active and break Si-O-Si bonds by creating two terminal Si-OH bonds, weakening the structure and establishing the mechanism that leads to hydroxyl groups at the crack tips of all the cracks studied, ultimately causing them to break. This behavior is attributed to the presence of microcracks. 1923567 of 87 surface cracks, created in a very short time (e.g., in milliseconds or seconds) during high-temperature forming and crack propagation assisted by atmospheric humidity. The industry uses various methods to improve the strength of glass, including ion exchange (chemical tempering), thermal tempering, lamination, etc. All of these methods have several shortcomings and limitations. For example, the widely used ion exchange and thermal tempering methods do not work below certain glass thicknesses and have compositional restrictions. By repairing the defects created by cooling the glass from the forming stage (molten glass temperatures) until it rapidly cools to room temperature, or well below Tg, the glass transition temperature (rigid glass temperatures), large stresses are created between the outer surface and the rapidly contracting interior, transgressing from the liquid to the solid state towards equilibrium (ambient) temperatures. These stresses are released, creating surface micro-cracks initiated by these stresses, and the water molecules present in the ambient air are the main source of crack propagation. All these effects reduce the strength of glass products. 1923567 of 87 200 times, or in other words, below 100% of theoretical mechanical strength to an actual approximation of 0.5% of theoretical mechanical strength. The three traditional methods for creating a protective compression layer depend on a certain physical thickness of the glass where the compression layer is developed. As the glass becomes thinner, the limit where compression layers are meaningful is exceeded. Protective glass used to be 0.7 mm thick, but it's moving towards 0.4 mm and even 0.2 mm. These decreasing thicknesses are approaching the limit of usefulness for ion exchange. Furthermore, in the case of smartphones, such as iPhones, the electronics are printed on a special alkali-free glass. Alkalis—for example, but not limited to, lithium, sodium, and potassium—are the main players in chemical tempering. However, these same ions will attack the transistors, liquid crystals, and electronics required for large flat-screen displays.Typical, regular, single-sheet substrates of flat glass (typically soda-lime or borosilicate) are traditionally produced with thicknesses from 3 mm to 15 mm, however, with a decreasing trend towards less than 3 mm. For flat glass with a thickness of 2 mm or less, tempering is reaching its physical limits. 1923567 of 87 example, glass less than 3 mm thick can hardly be tempered as ESG, therefore for thinner glass up to 2 mm thick, TVG is the traditional tempering grade possible. Inorganic coatings are inherently brittle and tend to develop microcracks during use. Non-brittle organic coatings, on the other hand, tend to be soft and are therefore susceptible to optical deterioration from abrasion during use. To date, no commercially available coating has the ability to create covalent bonds with the glass matrix by cracking the hydroxyl (OH-) groups on the glass surface, allowing bridging to an O-Si-O (or other) covalent bond, thus repairing the defects. Combining hardness with non-brittleness in the same material is extremely difficult. Therefore, there is a need for a coating that repairs glass surfaces from defects introduced during high-temperature forming, improving the strength of glass products while simultaneously providing sufficient abrasion resistance. SUMMARY OF THE INVENTION In the first aspect provided in this document, a method is given for preparing coatings for 1923567 of 87 improving the strength of glass and the fracture toughness of glass, comprising the mixing method a) a composition comprising 5-95% by weight of one or more alkoxysilane(s) of general formula RxSi(OR1)4-x with up to 40 wt% of one or more metal or metalloid oxide(s) and / or one or more metal or metalloid alkoxide(s) in the presence of up to 20 wt% of water and up to 95 wt% of an alcohol and up to 1 wt% of a catalyst, wherein R is an organic radical, R1 is independently selected from hydrogen and C1-18 alkyl, or isomers or polyvalences thereof, and x is an integer from 0 to 3; b) a composition comprising from 20 to 100% by weight of one or more metal or metalloid oxide(s) and / or one or more metal or metalloid alkoxide(s), up to 80% by weight of an alcohol, up to 20% by weight of water and up to 1% by weight of a catalyst; and c) a composition comprising up to 50% by weight of one or more metal or metalloid oxide(s) and / or one or more metal or metalloid alkoxide(s), up to 100% by weight of water and up to 100% by weight of an alcohol; where the weight percentage of a), b), c) and the mixture of the same, respectively, adds up to 100% by weight each. 1923567 of 87 In a second aspect provided in this document, a method is provided for preparing coatings to improve the strength and fracture toughness of glass, comprising the mixing method a) a composition comprising up to 25% by weight of one or more metal or metalloid oxide(s) and / or one or more metal or metalloid alkoxide(s) in the presence of up to 20% by weight of water and 60-95% by weight of an alcohol; b) a composition comprising 5-95% by weight of one or more alkoxysilane(s) of general formula RxSi(OR1)4-x where R is an organic radical, R1 is independently selected from hydrogen and C1-18 alkyl, or isomers or polyvalences thereof, and x is an integer from 0 to 3, 5-70% by weight of an alcohol, up to 20% by weight of water and up to 0.5% by weight of a catalyst; and c) a composition comprising 10-50% by weight of one or more metal or metalloid oxide(s) and / or one or more metal or metalloid alkoxide(s), 10-90% by weight of water and up to 100% by weight of an alcohol; where the weight percentage of a), b), c) and the mixture of the same, respectively, adds up to 100% by weight. 1923567 of 87 In one embodiment of the present invention, the catalyst is nitric acid, aqua regia, or hydrofluoric acid, or a combination thereof. In one embodiment of the present invention, R is selected from C1-18 alkyl, C1-18 heteroalkyl, and alkoxy groups. C1-18, C2-18 alkene, phenyl, R2-(CH2)n-, cycloalkyl and aryl, and R2-O-(CH2)n, or isomers or polyvalents thereof; R1 is a C1-18 alkyl or cycloalkyl, or isomers or polyvalents thereof; R2 is independently selected from hydrogen, C1-18 alkyl, (C2H4O)-(R3)m-, C2-18 alkene, or isomers or polyvalents thereof; R3 is independently selected from C1-18 alkyl, or isomers or polyvalents thereof; n is an integer from 0 to 10; and m is an integer from 0 to 10. In a further embodiment of the present invention one or more alkoxysilane(s) are selected from βglycidoxypropyltrimethoxysilane, yglycidoxypropyltrimethoxysilane, y-methacryloxypropylsilane, methoxyethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, ethyltrimethoxysilane, diethyldimethoxysilane and triethylmethoxysilane. In a further embodiment of the present invention, the one or more metal or metalloid oxide(s) and / or the one or more 7 1923567 of 87 metal or metalloid alkoxide(s) are selected from oxides and / or alkoxides of boron, aluminum, gallium, indium, thallium, silicon, germanium, tin, lead, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, copper, silver, gold, palladium, platinum, zinc, cobalt, rhodium, iridium, selenium, tellurium or polonium, or even other species. In a further embodiment of the present invention, the alkoxysilane is β-glycidoxypropyltrimethoxysilane or γ-glycidoxypropyltrimethoxysilane and the metal alkoxide is selected from boron alkoxides, titanium alkoxides and silicon alkoxides or mixtures thereof. In a third aspect, the present invention is directed to a coating prepared by the method provided herein. In a fourth aspect, the present invention relates to a coating comprising a mixture of a) a composition comprising 50-85 wt% of one or more alkoxysilane(s) of general formula RxSi(OR1)4-x with up to 35 wt% of one or more metal or metalloid oxide(s) and / or one or more metal or metalloid alkoxide(s) in the presence of up to 10 wt% of water and up to 30 wt% of an alcohol and up to 1 wt% of a catalyst, wherein R is an organic radical, R1 is selected 8 1923567 of 87 independently of hydrogen and C1-18 alkyl, or isomers or polyvalences thereof, yx is an integer from 0 to 3; b) a composition comprising 20-100% by weight of one or more metal or metalloid oxide(s) and / or one or more metal or metalloid alkoxide(s), up to 80% by weight of an alcohol, up to 20% by weight of water and up to 1% by weight of a catalyst; and c) a composition comprising up to 50% by weight of one or more metal or metalloid oxide(s) and / or one or more metal or metalloid alkoxide(s), up to 100% by weight of water and up to 100% by weight of an alcohol; where the weight percentage of a), b), c) and the mixture of the same, respectively, adds up to 100% by weight. In a fifth aspect, the present invention is directed to the use of the coating provided herein to improve the strength of glass and the fracture toughness of glass, wherein the strength of glass and the fracture toughness are improved by repairing cracks in the surface of the glass. In a sixth aspect, the present invention is directed to the use of the coating provided herein for repairing damaged silica-containing material, which includes, among others, any glass. 1923567 of 87 In one embodiment, the present invention is directed to the use provided for herein, wherein the silica-containing materials comprise glass, ceramics, glass-ceramics, quartz, cement, and concrete. In one embodiment, the present invention is directed to the use provided herein, in which one or more additional coatings are applied to improve abrasion resistance, chemical resistance, birefringence, refractive index modification, hardness increase, protection of photovoltaic or semiconductor devices from potential-induced degradation, control of mechanical strength increase, water repellency by improving hydrophobicity, improving oliophobicity, protection against staining, weathering and / or damage resulting from energy release at the breaking point. In a further embodiment, the present invention is directed to the use provided herein, wherein one or more coatings are applied by dip coating, spray coating, vapor deposition, misting, external plasma deposition, chemical vapor deposition, plasma-induced vapor deposition, absorption, soaking, suspension and / or plasma-enhanced vapor deposition. 1923567 of 87 In a further embodiment, the present invention is directed to the use provided herein, in which one or more coatings are applied in a controlled atmosphere by pressures below or above atmospheric pressure and / or at temperatures above or below atmospheric temperature. In a further embodiment, the present invention is directed to the use provided herein, wherein the controlled atmosphere comprises air conditioning with a dew point below -20°C (253K), below -50°C (223K), below -78.5°C (194.7K), below -195.8°C (77.35K), below 27K, or to 4K. In a further embodiment, the present invention is directed to the use provided herein, wherein the controlled atmosphere comprises an industrial or special gas. In a further embodiment, the present invention is directed to the use provided herein, wherein the pressure during any of the processes involved in the present invention comprises a pressure up to ambient pressure, an absolute pressure up to 950 hPa, below 500 hPa, below 100 hPa, below 1923567 of 87 of 10 hPa, below 1 hPa, below 0.1 Pa, less than 10-6Pa, or even less than 10-9Pa. In a further embodiment, the present invention is directed to the use provided herein, wherein the unused coating is removed from the surface of the glass. In a further embodiment, the present invention is directed to the use provided herein, wherein the unused coating is removed by immersing the coated glass or rinsing the coated glass with a solvent. In a further embodiment, the present invention is directed to the use provided herein, wherein the improvement in the strength of the glass is between 50 and 5000%, above 5000% or above 10000%. In a further embodiment, the present invention is directed to the use provided herein, in which devitrification is avoided. In another embodiment, the present invention is directed to the use provided herein, in which the damage is induced by physical and / or chemical impact. In another embodiment, the present invention is directed to the use provided herein, wherein prior to applying the coating, the glass surface, 1923567 of 87, including optionally the edges, is pre-treated with fluoric acid, with mechanical edge grinding, with flame polishing, with laser treatment and / or with any other edge treatment technology. In another embodiment, the present invention is directed to the use provided herein, wherein prior to applying the coating, the glass is exposed to a temperature of at least 300 K below the transformation temperature (Tg). In a further embodiment, the present invention is directed to the use provided herein, in which a temperature of at least 30°C is applied to the coated glass or to the coated silica-containing material for curing. In another embodiment, the present invention is directed to the use provided herein, wherein the coated glass or the coated silica-containing material is exposed to waves of suitable frequency and / or wavelength comprising subsonic, sonic, supersonic, infrared, visible, ultraviolet, extreme ultraviolet range and / or wavelengths lower than the extreme ultraviolet range, and / or any other suitable frequency and / or wavelength that triggers the desired reaction between the reactants depending on the physical properties, 1923567 of 87 whatever the frequency, to allow the curing of the coating of the glass substrate, the silica-containing material. In a further embodiment, the present invention is directed to the use provided herein, wherein the coated glass or silica-containing material is subjected to tempering before or after coating. In one embodiment, the present invention is directed to the use of the coating provided herein, wherein the silica-containing material is in the form of a porous material or powder that is soaked into the coating partly or completely along the pores or within the powder cluster. In a seventh aspect, the present invention is directed to a glass product or a product made of silica-containing material prepared by the use described herein. In a further embodiment, new bottles (containers) or returnable bottles (containers) with physical or chemical surface damage can be repaired by preparing them using any of the selected uses described herein, so that such bottles can be reused for at least one (1) cycle 1923567 of 87 additional, such as for example another 5 cycles or 10 cycles or even more cycles. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1a shows the reaction scheme for a specific alkoxysilane with water in the presence of an acid catalyst; Fig. 1b shows the reaction of the reaction product of Figure 1a with a specific titanium alkoxide; Fig. 2 is a schematic representation of the chemical bonding of the inventive coating on a glass surface (a) and a schematic representation of the immobilization of sodium ions by boron coordination change (b); Fig. 3 shows the strength distribution curves of coated and uncoated samples; Fig. 4 shows graphs indicating that the strength of float glass samples increases when the tin and air surfaces are coated as measured by the cone cracking load technique. Fig. 5a shows a fracture pattern of uncoated glass; Fig. 5b shows an exemplary fracture model of coated glass according to the invention; 1923567 of 87 Figure 6 shows the sodium leaching of coated and uncoated glass, where the coating contains boron; Figure 7 shows a sample of a glass produced entirely using the sol-gel process of the invention. Fig. 8 shows glass damaged by a Vickers impression test: different illumination under the microscope; Fig. 9 shows sample images of uncoated (left) and coated (far right) Vickers impressions, and average break test results; Fig 10 is a Vickers impression surface analysis on a float glass sample; Fig. 11 shows the break test values ​​(1) for uncoated glass without mechanically induced defects, (2) for uncoated glass with mechanically induced defects, and (3) for glass samples with mechanically induced defects that have been coated after the application of the defects. DETAILED DESCRIPTION The present invention provides a sol-gel composition in the form of a coating as provided herein, which is an organic-inorganic polymer that transforms into a true amorphous glass network that 1923567 of 87 repairs defects introduced by rapid cooling and differential expansion. In particular, the present invention is directed to a method for repairing coatings to improve the strength and fracture toughness of glass, the method comprising mixing a) a composition comprising 5-95 wt% of one or more alkoxysilane(s) of general formula RxSi(OR1)4-x with up to 40 wt% of one or more metal or metalloid oxide(s) and / or one or more metal or metalloid alkoxide(s) in the presence of up to 20 wt% of water and up to 95 wt% of an alcohol and up to 1 wt% of a catalyst, wherein R is an organic radical, R1 is independently selected from hydrogen and C1-18 alkyl, or isomers or polyvalences thereof, and x is an integer from 0 to 3; b) a composition comprising 20-100% by weight of one or more metal or metalloid oxide(s) and / or one or more metal or metalloid alkoxide(s), up to 80% by weight of an alcohol, up to 20% by weight of water and up to 1% by weight of a catalyst; and c) a composition comprising up to 50% by weight of one or more metal or metalloid oxide(s) and / or one or more metal or metalloid alkoxide(s), up to 100% by weight of water and up to 100% by weight of an alcohol; 1923567 of 87 where the weight percentage of a), b), c) and the mixture of the same, respectively, adds up to 100% by weight. In one embodiment, the method comprises mixing a) a composition comprising 20-80% by weight of one or more alkoxysilane(s) of general formula RxSi(OR1)4-x with up to 30 wt% of one or more metal or metalloid oxide(s) and / or one or more metal or metalloid alkoxide(s) in the presence of up to 15 wt% of water and up to 50 wt% of an alcohol and up to 1 wt% of a catalyst, wherein R is an organic radical, R1 is independently selected from hydrogen and C1-18 alkyl, or isomers or polyvalences thereof, and x is an integer from 0 to 3; b) a composition comprising from 30 to 100% by weight of one or more metal or metalloid oxide(s) and / or one or more metal or metalloid alkoxide(s), up to 60% by weight of an alcohol, up to 10% by weight of water and up to 1% by weight of a catalyst; and c) a composition comprising up to 30% by weight of one or more metal or metalloid oxide(s) and / or one or more metal or metalloid alkoxide(s), up to 100% by weight of water and up to 100% by weight of an alcohol; 1923567 of 87 where the weight percentage of a), b), c) and the mixture of the same, respectively, adds up to 100% by weight. In another embodiment, the method comprises mixing a) a composition comprising 50-80% by weight of one or more alkoxysilane(s) of general formula RxSi(OR1)4-x with up to 25% by weight of one or more metal or metalloid oxide(s) and / or one or more metal or metalloid alkoxide(s) in the presence of up to 10% by weight of water and up to 40% by weight of an alcohol and up to 1% by weight of a catalyst, wherein R is an organic radical, R1 is independently selected from hydrogen and C1-18 alkyl, or isomers or polyvalences thereof, and x is an integer from 0 to 3; b) a composition comprising 40-100% by weight of one or more metal or metalloid oxide(s) and / or one or more metal or metalloid alkoxide(s), up to 50% by weight of an alcohol, up to 10% by weight of water and up to 1% by weight of a catalyst; and c) a composition comprising up to 25% by weight of one or more metal or metalloid oxide(s) and / or one or more metal or metalloid alkoxide(s), up to 100% by weight of water and up to 100% by weight of an alcohol; where the weight percentage of a), b), c) and the mixture of the same, respectively, adds up to 100% by weight. 1923567 of 87 In yet another embodiment, the method comprises mixing a) a composition comprising 60-75% by weight of one or more alkoxysilane(s) of general formula RxSi(OR1)4-x with up to 20 wt% of one or more metal or metalloid oxide(s) and / or one or more metal or metalloid alkoxide(s) in the presence of 5-10 wt% of water and up to 30 wt% of an alcohol and up to 1 wt% of a catalyst, wherein R is an organic radical, R1 is independently selected from hydrogen and C1-18 alkyl, or isomers or polyvalences thereof, and x is an integer from 0 to 3; b) a composition comprising 50-100% by weight of one or more metal or metalloid oxide(s) and / or one or more metal or metalloid alkoxide(s), up to 40% by weight of an alcohol, up to 5% by weight of water and up to 1% by weight of a catalyst; and c) a composition comprising up to 20% by weight of one or more metal or metalloid oxide(s) and / or one or more metal or metalloid alkoxide(s), up to 100% by weight of water and up to 100% by weight of an alcohol; where the weight percentage of a), b), c) and the mixture of the same, respectively, adds up to 100% by weight. The individual absolute weights of compositions a), b), and c) result in a total combined weight, the relative weights of a) + b) + c) being 100%, the ratio of a), 1923567 of 87 b), and c), respectively, individually typically range from 20 to 70% by weight for a), from 5 to 40% by weight for b), and from 0 to 50% by weight for c). In one embodiment of the invention, the compositions are used in a proportion of 30-65% by weight of composition a), 5-35% by weight of composition b), and up to 50% by weight of composition c). For example, the compositions are used in a proportion of 40-65% by weight of composition a), 10-35% by weight of composition b), and up to 50% by weight of composition c). In another embodiment, the compositions are used in a proportion of 40-45% by weight of composition a), 10-15% by weight of composition b), and 10-50% by weight of composition c). The sum of the amounts of compositions a), b), and c) totals 100% by weight. The present invention recognizes that the strength of glass deteriorates drastically upon contact with the moisture in the air at forming temperatures, and when water is chemically active, forming chemical bonds with the glass by breaking Si-O-Si bonds and forming terminal Si-OH bonds, which are weak points in the surface structure, and manipulating and forcing the creation of surface microcracks. Known and practiced glass strengthening methods work by creating a surface compression layer that must be overcome. 1923567 of 87 before breakage occurs. The present invention describes the first method for truly repairing surface defects, the creation of which is common to all glass produced in the last 5,000 years. The use of the coating provided herein significantly improves the strength of the glass and its fracture toughness. The coating bonds covalently to the glass surface after application, eradicating existing surface microcracks and preventing their future formation, as well as preventing deterioration of strength due to handling and atmospheric humidity.Since surface cracks or defects are small—for example, with a diameter on the micrometer or nanometer scale, or even smaller—after the coating has penetrated the surface defects, it can be removed with solvents before thermal curing, leaving the surface as pristine as new glass. However, the micro-defect retains enough polymer to become glass during curing and repair the surface defect; that is, to integrate into the glass matrix by forming covalent bonds between one or more coatings and the glass material. Therefore, without wishing to be too theoretical, covalent bonds between the coating and the glass can be created by means of... 1923567 of 87 A chemical reaction by cracking the (terminal) hydroxyl groups (OH-) on the glass surface, allowing bridging to a covalent [-O-Si-] bond or any other covalent bond. In other words, the terminal hydroxyl groups on the uncoated glass surface are cracked by chemical reaction with one or more coatings, and covalent bonds are formed between the reactive part of one or more coatings and the oxygen atoms on the glass surface resulting from the cracking of the hydroxyl groups. Any of the inventive coatings (coating solutions) penetrates the microcracks on the glass surface and bonds to the terminal hydroxyl groups of the glass matrix, and in subsequent steps, these hydroxyl groups are broken, creating a new chemical covalent bond.Furthermore, the coating has the remarkable properties of being non-brittle (it does not develop its own surface cracks) yet virtually as hard and abrasion-resistant as the unaltered glass surface. Therefore, the use of the coating—that is, the hybrid copolymer (a polymer of organic and inorganic elements)—provides maximized hardness with sufficient ductility to prevent crack propagation. The coating has the advantage. 1923567 of 87 additional to be soluble to facilitate coating and curing. A limiting factor in the creation of true glass is the temperature of the liquid—that point in cooling where the first crystal forms, or where, upon heating, the last crystal dissolves. From the periodic table and the list of metal oxides that can be used to produce glass, there is a significant limitation on the quantity of these metal oxides that will form viable glasses without devitrification (i.e., without crystallizing). The present invention introduces a substantial increase in the availability and concentration of metal oxides that can be incorporated into thin films or bulk glass products. Since the conversion to true amorphous glass occurs below 500°C, this is lower than the temperatures at which devitrification is a concern.The new materials can create glasses with extremely high refractive indices or other physical properties that were never before available to scientists working with true inorganic glasses. An example can be seen in Fig. 7, where the glass on the left is an alumina sol-gel with 64% voids, but less than 50 Å in diameter (the sample on the right was immersed in isopropyl alcohol to increase transparency; photograph taken). 1923567 of 87 directly after immersion; ethanol is even better due to its smaller molecule size). Therefore, with the present invention, devitrification is avoided or even excluded. This sample was produced entirely using the sol-gel process without coating. However, the same sample and formulations can be used to produce coatings with a very high Al2O3 content, which is not possible using regular glass melting processes, as it would devitrify or crystallize. With the present invention, it is possible to increase the functionality and versatility of glass to the point where it can replace other materials. For example, due to the greater mechanical strength of glass, the wall thickness of glass containers can be greatly reduced, and consequently, the weight, resulting in a significant reduction in the carbon footprint as the amount of energy required to produce a container is substantially reduced. This weight reduction also contributes to the possibility that plastic bottles, which are filling and polluting our planet, may become obsolete or at least be largely replaced. Furthermore, the productivity of the glass furnace increases considerably as more containers can be produced per unit of glass melting area. 1923567 of 87 In another embodiment, prior to applying the coating, the surface of the glass substrate is treated with hydrofluoric acid to remove a first layer from the glass surface, thereby reducing the depth of the microcracks and eliminating some of the terminal Si-OH bonds. In this embodiment, the coating applied after this treatment will result in improved crack penetration efficiency and, consequently, a greater increase in mechanical strength. With the present invention, any of the foregoing or described herein is also suitable for a silica-containing material defined below. In one aspect of the present invention, it is also possible to repair damaged silica-containing materials. Such silica-containing material may be, among others, glass, ceramics, glass-ceramics, quartz, cement, and concrete. The silica-containing materials may be in any suitable form, such as, but not limited to, solid form, compressed or sintered powders, or porous materials. In a preferred embodiment, the silica-containing material is glass. In the process of repairing such silica-containing materials, cracks and / or damage on the surface, or, if they have any surface outlet, materially within the silica-containing material, can be repaired. 1923567 of 87 repairing using the inventive coating described herein, so that the glass recovers at least most of its previous properties, such as glass strength and fracture toughness, or these properties are even improved. With the present invention, for example, damage induced by physical and / or chemical impact can be repaired.Non-limiting examples of such damage include fractures caused by hail, gravel, rocks, stones, or other physical objects; differential temperature impact; fatigue failure, such as from alternating stresses; or any other physical impact on glass, windows, photovoltaic panels, automotive glass (e.g., windshields), container glass, tubular glass, crystal glass, tableware glass, heat-resistant glass, glass-ceramics, optical glass, or any other glass substrates, quartz substrates, ceramic substrates, or substrates containing cement or concrete. In another aspect of this invention, surface damage that occurs during the various use cycles of returnable bottles (containers) can be repaired so that the original mechanical strength of the bottles (containers) is restored. 1923567 of 87 applying the present invention. Damage induced by any other impact is also covered by the present invention. As mentioned previously, by applying—and if necessary—curing the coating of the invention, the properties of the damaged silica-containing material can be largely, almost completely, or completely restored. For example, the mechanical strength of glass can be restored to at least 50% of its remaining strength, such as at least 60%, at least 75%, at least 80%, at least 90%, 100%, or even more than 100%. The same applies to other silica-containing materials. With the coating of the present invention, damaged materials containing silica can be repaired within the limits of visibility to the naked eye and / or even within the visibility of a magnifying device, such as a microscope or similar. In a first step of the inventive method, composition a) is prepared by mixing the components in a suitable container. The alkoxysilane compound is partially hydrolyzed using a catalyst in the presence of water. The water in this step and in all subsequent steps of the inventive method can be any water, such as water 1923567 of 87 deionized, distilled water, multi-distilled water, for example, double-distilled water, heavy water, or the like. At most, stoichiometric amounts of water are used, for example, one mole of water per mole of reactant group. The catalyst can be selected from any catalyst suitable for this type of chemical reaction. In the present invention, the catalyst can be consumed during the reaction. For example, the catalyst comprises an activator (chemical reaction) or an acid, such as, among others, nitric acid, aqua regia, hydrochloric acid, sulfuric acid, or the like, and mixtures thereof. In a preferred embodiment, the catalyst is nitric acid, aqua regia, hydrofluoric acid, or a combination thereof. This reaction leads to the formation of hydroxyl groups that react with one or more metal or metalloid oxide(s) and / or metal or metalloid alkoxide(s) and / or a silane. Sufficient time must be allowed for the hydrolysis reaction to consume all the water introduced into the system, ensuring that no free water remains in the solution for the next reaction step. This reaction consumes all the added water quickly and creates terminal hydroxyl bonds. Excessive time between the two reactions must be avoided, otherwise the alkoxysilane will decompose. The hydrolyzed composition 1923567 will self-polymerize slowly, which will negatively affect homogeneity. According to one embodiment of the invention, the reaction time between the alkoxysilane and water can be less than 60 minutes, such as less than 30 minutes, less than 20 minutes, less than 15 minutes, less than 10 minutes, less than 5 minutes, or even less than 1 minute. For example, the reaction time can be between 5 and 10 minutes, such as 6 to 10 minutes or 8 to 10 minutes. In one embodiment, the reaction time is less than 10 minutes. In another embodiment, composition a) can be allowed to stand overnight. In general, step a) can be carried out under ambient conditions, such as at room temperature. In a preferred embodiment, step a) can be carried out under a controlled atmosphere, such as a water vapor-free atmosphere, an oxygen-free atmosphere, or an inert atmosphere as described below. In the second step, composition b) is premixed and gradually added to the mixture obtained in step a) of the inventive method. The metal or metalloid oxide(s) and / or the metal or metalloid alkoxide(s) must be introduced within a critical time frame to prevent significant self-polymerization of the partially hydrolyzed alkoxysilane. Fig. 1b shows a reaction 1923567 of 87 specimens between the compound obtained in Fig. 1a and Ti(OC3H7)4. Under these circumstances, for example, when titanium alkoxide is introduced into the solution, it can only react with the hydroxyl groups of glycidoxypropyltrimethoxysilane, thereby linking the organic and inorganic components into a copolymer chain. This creates oxide bonds between organic and inorganic groups in a hybrid polymer solution (in soluble form). In a different embodiment, composition b) is not premixed, but is mixed with composition a) by spraying the pure composition b) into the pure spray mist of composition a), or vice versa, when the components are applied to the glass of the glass-ceramic substrate. At this stage, it is important that no free water is present in the mixture at the end of the first part of the reaction; otherwise, the metal alkoxide will react with the free water and condense or precipitate separately. Secondly, and more importantly, excessive time between the two reactions must be avoided, as this will cause the hydrolyzed alkoxysilane to slowly self-polymerize, negatively impacting homogeneity. The second part of the reaction has a minimal time requirement, but unlike the first part, 1923567 of 87 does not have a maximum time requirement. Most of the remaining alkoxy bonds of the copolymer can be formed at any time with further additions of water. Additional water addition leads to the formation of a hard, abrasion-resistant structure by removing excess organic groups and facilitating the formation of longer oxide network chains. However, there is a limit to the amount of water added, for example, around 50% of the total volume, that the system can tolerate without causing turbidity of the solution due to the solvent's insolubility in water. After this bonding, the product shown in Fig. 1b is fully hydrolyzable to produce homogeneous inorganic-organic copolymers without fear of segregation or precipitation with further additions of water. The resulting polymer is soluble in water and alcohol, so it can be diluted to any concentration to deposit the desired film thickness on glass. Step (b) of the inventive method can be carried out in less than 60 minutes, such as less than 30 minutes, less than 20 minutes, less than 15 minutes, less than 10 minutes, less than 5 minutes, or even less than 1 minute. For example, the reaction time can be between 5 and 10 minutes, such as 6 to 10 minutes or 8 to 10 minutes. 1923567 of 87 to step a), the reaction can be carried out under ambient conditions, such as for example at room temperature. In a preferred embodiment, step b) can be carried out in a water vapor-free or inert atmosphere, such as an oxygen-free atmosphere or an inert atmosphere as described below. In the third step, composition c) is added and the reaction mixture is stirred. This third step c) may be an optional step in the inventive preparation process. Step c) can also be carried out in less than 60 minutes, such as less than 30 minutes, less than 15 minutes, less than 10 minutes, less than 5 minutes, or even less than 1 minute. For example, the reaction time can be between 5 and 10 minutes, such as 6 to 10 minutes or 8 to 10 minutes. Regarding steps a) and b), the reaction can be carried out under ambient conditions, such as at room temperature. In a preferred embodiment, step a) can be carried out under a water vapor-free atmosphere, an inert atmosphere such as an oxygen-free atmosphere, or an inert atmosphere as described below. In an alternative aspect, the present invention relates to a method for preparing coatings for 1923567 of 87 to improve the strength and fracture toughness of glass, the method comprises mixing a) a composition comprising up to 25% by weight of one or more metal or metalloid oxide(s) and / or one or more metal or metalloid alkoxide(s) in the presence of up to 20% by weight of water and 60-95% by weight of an alcohol; b) a composition comprising 5-95% by weight of one or more alkoxysilane(s) of general formula RxSi(OR1)4-x where R is an organic radical, R1 is independently selected from hydrogen and C1-18 alkyl, or isomers or polyvalences thereof, and x is an integer from 0 to 3, 5-70% by weight of an alcohol, up to 20% by weight of water and up to 0.5% by weight of a catalyst; and c) a composition comprising 10-50% by weight of one or more metal or metalloid oxide(s) and / or one or more metal or metalloid alkoxide(s), 10-90% by weight of water and up to 100% by weight of an alcohol; where the weight percentage of a), b), c) and the mixture of the same, respectively, adds up to 100% by weight. In this aspect of the present invention, the same reaction conditions as described above are generally used. The individual absolute weights of compositions a), b), and c) result in a weight 1923567 of 87 combined total, the relative weights of a) + b) + c) being 100%, the proportions of a), b), and c) typically range individually, respectively, for a) from 20 to 70% by weight, for b) from 5 to 40% by weight, and for c) from 0 to 50%. In one embodiment of the invention, the compositions are used in a proportion of 30-65% by weight of composition a), 5-35% by weight of composition b), and up to 50% by weight of composition c). For example, the compositions are used in a proportion of 40-65% by weight of composition a), 10-35% by weight of composition b), and up to 50% by weight of composition c). In another embodiment, the compositions are used in a proportion of 40-45% by weight of composition a), 10-15% by weight of composition b) and 10-50% by weight of composition c). The sum of the amounts of compositions a), b) and c) totals 100% by weight. In one embodiment of this aspect of the present invention, composition a) is prepared and applied using a coating technique described below and subsequently cured. In a further step, composition b) is prepared and composition c) is gradually added. The mixture of compositions b) and c) is then applied onto the glass coated with composition a) using a coating technique described below and 1923567 of 87 is subsequently cured. In one embodiment, composition a) is applied, then the mixture of compositions b) and c) is applied, and the curing step is carried out. In an embodiment of the above, composition a) ob) comprises 50-90% by weight of one or more alkoxysilane(s). In an embodiment of the above, composition a) ob) comprises 65-75% by weight of one or more alkoxysilane(s). In an embodiment of the above, the composition a), b), and oc) independently comprises 1–30% by weight of one or more metal or metalloid oxide(s) and / or one or more metal or metalloid alkoxide(s), if present. In an embodiment of the above, the composition a), b), and oc) independently comprises 5–25% by weight of one or more metal or metalloid oxide(s) and / or one or more metal or metalloid alkoxide(s), if present. In one embodiment of the aspects provided herein, the catalyst is present in an amount of 0.1-1% by weight. In another embodiment of the aspects provided herein, the catalyst is present in an amount of 0.1-0.5% by weight. 1923567 of 87 In an implementation of the aspects provided in this document, the amount of water present is > 0% by weight and within the ranges provided in this document. In an embodiment of the aspects provided above, composition a) is present from 20 to 70% by weight. In an embodiment of the aspects provided above, composition a) is present from 30 to 65% by weight. In an embodiment of the aspects provided above, composition a) is present from 40 to 65% by weight. In an embodiment of the aspects provided above, composition a) is present from 40 to 66% by weight. In an embodiment of the aspects provided above, composition a) is present from 40 to 50% by weight. In an embodiment of the aspects provided above, composition b) is present from 5 to 40% by weight. In an embodiment of the aspects provided above, composition b) is present from 5 to 35% by weight. In an embodiment of the aspects provided above, composition b) is present from 10 to 35% by weight. In an embodiment of the aspects provided above, composition b) is present from 10 to 30% by weight. In an embodiment of the aspects provided 1923567 of 87 above, composition b) is present from 10 to 25% by weight. In an embodiment of the aspects provided above, composition c) is present from 0 to 50% by weight. In an embodiment of the aspects provided above, composition c) is present from 5 to 50% by weight. In an embodiment of the aspects provided above, composition c) is present from 10 to 50% by weight. In an embodiment of the aspects provided above, composition c) is present from 15 to 50% by weight. In an embodiment of the aspects provided above, composition c) is present from 20 to 50% by weight. The present invention covers any combination of the above quantities. The alkoxysilane to be used in the invention provided herein may generally be any alkoxysilane that can react with one or more metal or metalloid oxide(s) and / or metal or metalloid alkoxide(s), i.e., that has reactive groups or can provide reactive groups upon reaction with water. In one embodiment, one or more alkoxysilanes may be selected from the general formula RxSi(OR1)4-x. 1923567 of 87 R can be selected from an organic radical, such as, for example, but not limited to, C1-18 alkyl, C1-18 heteroalkyl, C1-18 alkoxy, C2-18 alkene, phenyl, R2(CH2)n- and R2-O-(CH2)n, or isomers or polyvalents thereof. A C1-18 alkyl group is a non-cyclic saturated hydrocarbon with a linear or branched chain that has, for example, 1 to 18 carbon atoms, 1 to 15 carbon atoms, 1 to 12 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, 1 to 4 carbon atoms, 1 to 3 carbon atoms, 2 carbon atoms, or just 1 carbon atom. The alkyl group may be selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, t-pentyl, neopentyl, i-pentyl, s-pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecil, hexadecyl, heptadecyl, and octadecyl, or isomers or polyvalents thereof, but is not limited to them. The alkyl group may optionally be substituted with other alkyl groups, hydrogen, halogen, and / or -CN, or the like. A C1-18 heteroalkyl group is a C1-18 alkyl group as defined above, in which one or more carbon atoms are substituted with selected heteroatoms 1923567 of 87 regardless of the group consisting of oxygen, sulfur and / or silicon. A C1-18 alkoxy group is an alkyl group, as defined above, singletly bonded to oxygen. Representative alkoxy groups include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, and n-butoxy. A C2-18 alkene group is an unsaturated hydrocarbon having from 2 to 18 carbon atoms and having one or more carbon-carbon double bonds, such as, but not limited to, -CH=CH2, -CH=CH-CH3, -CH2-CH=CH2, -CH=CH-CH2CH3, -CH=CH-CH=CH2 and the like. The alkene group may be optionally substituted with other alkyl groups, hydrogen, halogen, and / or -CN and the like. R2 in the above formulas can be hydrogen, Cl-18 alkyl, (C2H4O)-(R3)m- or C2-18 alkene, or isomers or polyvalents thereof. In one embodiment, R2 can be (C2H4O)CH2-O-(CH2)3-. R3 can be selected independently of alkyl Cl-18, or isomers or polyvalences thereof. X can be an integer from 0 to 3, for example, x can be 1, 2, or 3. n can be an integer from 0 to 10, such as 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. m can be a number from 0 to 10, such as 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. 1923567 of 87 In a preferred embodiment, short-chain polymer molecules are used to allow better penetration into the microcracks. In a further embodiment, the short-chain polymer coating material can be introduced first to allow better penetration toward the tip of the microcrack, followed by a second coating on top of the first, which uniformly fills the remaining gaps. Applying this technique creates the maximum possible coverage of reactants, i.e., chemical compounds coated with the terminating Si-OH bond. In this regard, the short-chain polymer molecules can have an alkyl, heteroalkyl, alkoxy, or alkene group having fewer than 18 carbon atoms, such as fewer than 15 carbon atoms, fewer than 8 carbon atoms, fewer than 15 carbon atoms, or even fewer. In one embodiment, the alkoxysilane(s) are selected from glycidoxypropyltrimethoxysilanes, such as (1) β-glycidoxypropyltrimethoxysilane or (2) γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropylsilane, methoxyethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, ethyltrimethoxysilane, diethyldimethoxysilane, and triethylmethoxysilane. In one embodiment, the alkoxysilane is 41 1923567 of 87 a glycidoxypropyltrimethoxysilane. In a preferred embodiment, the alkoxysilane is yglycidoxypropyltrimethoxysilane. These chemicals are many and varied and can be purchased from any number of chemical supply companies. The one or more metal or metalloid oxide(s) and / or one or more metal or metalloid alkoxide(s) can generally be selected from any metal compound that can react with one or more alkoxysilane(s). For example, the metal component of these compounds can be selected from, but is not limited to, boron, aluminum, gallium, indium, thallium, silicon, germanium, tin, lead, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, copper, silver, gold, palladium, platinum, zinc, cobalt, rhodium, iridium, selenium, tellurium, or polonium. In one embodiment, the one or more metal or metalloid oxide(s) and / or one or more metal or metalloid alkoxide(s) are selected from oxides and / or alkoxides of aluminum, silicon, and / or titanium. In one embodiment, the metal is titanium and / or silicon.The alkyl part of the alkoxy group can be selected from methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, t-pentyl, neo-pentyl, i-pentyl, spentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecil, hexadecyl. 1923567 of 87 heptadecyl and octadecyl, or isomers or polyvalences thereof, but not limited to them. In a further embodiment, the metal alkoxide may be, but is not limited to, B(OCH3)3, B(OC2H5)3, B(OC3H7)3, Ti(OCH3)4, Ti(OC2H5)4, Ti(OC3H7)4, Ti(OC4H9)4, Zr(OC2H5)4, Zr(OC3H7)4, Zr(OC4H9)4, Al(OC2H5)3, Al(OC3H7)3, Al(OC4H9)3, Si(OCH3)4, Si(OC2H5)4, Si(OC3H7)4, CH3Si(CH3)3, or (CH3)2Si(OCH3)Cl, or in place of the metals described above, any other metal. The alkyl group may optionally be substituted with a halogen, such as fluorine, chlorine, bromine, or iodine. In one embodiment, the alkoxysilane is reacted with at least two different metal compounds selected from any of the metal and / or metalloid oxide(s) defined above and / or metal and / or metalloid alkoxide(s). In one embodiment, one of the at least two different metal compounds is a silicon compound. In one embodiment, the metal or metalloid oxide(s) mentioned above and / or the metal or metalloid alkoxide(s) is / are not an oxide and / or alkoxide of cer. In one embodiment, the metal or metalloid oxide(s) mentioned above and / or the metal or metalloid alkoxide(s) is / are not an oxide and / or alkoxide of tin. In one embodiment, the metal or metalloid oxide(s) 1923567 of the 87 mentioned above and / or the metal or metalloid alkoxide(s) is not an aluminum oxide and / or alkoxide. In one embodiment, the alkoxysilane is β-glycidoxypropyltrimethoxysilane, and one or more metal or metalloid alkoxide(s) are selected from titanium alkoxide(s) and / or silicon alkoxide(s). For example, the alkoxysilane may be β-glycidoxypropyltrimethoxysilane and the one or more metal alkoxide(s) may be, but are not limited to, B(OCH3)3, Ti(OC2H5)4, Ti(OC3H7)4, Si(OCH3)4, Si(OC2H5)4, CH3Si(CH3)3, or (CH3)2Si(OCH3)Cl, or any other metal mentioned above. In one embodiment, the alkoxysilane is γglycidoxypropyltrimethoxysilane and one or more metal alkoxide(s) are B(OCH3)3, Ti(OC2H5)4, Ti(OC3H7)4, Si(OCH3)4, Si(OC2H5)4, CH3Si(CH3)3, or (CH3)2Si(OCH3)Cl. In another embodiment, the coating to be used is the hydrolytic polycondensation product of γ-glycidoxypropyltrimethoxysilane with titanium alkoxides. The coating provided can be made hydrophobic when the respective metal compounds contain some alkyl linkages instead of possessing only alkoxy linkages. The alkyl linkages in these compounds are inert, remaining as terminally stable groups with their hydrophobic properties. Hydrophobicity can also be induced in the coating by including soluble or dispersible fluorine compounds in the precursor coating solution. Fluorine compounds generally used in this field can be used in the coating of the invention, such as, for example, fluorinated alkyl or alkoxy groups, but are not limited to them. Exemplary coatings used according to the invention may be, but are not limited to, water- glycidoxypropyltrimethoxysilane 100 g Ethanol 25 g Si(OC2H5)4 0 to 25 g Water 10 to 12 g HNO3 0 to 0.3 g TUOC2H5) 4 25 to 40 g Water (solvent) 20 to 150 g Ethanol (solvent) 0 to 100 g y- glycidoxypropyltrimethoxysilane) 8 g Ethanol 25 g 1923567 of H2O 8 g HNO3 0.5 g Ti(OC2H5) 4 40 g H2O (solvent) 150 g y- glycidoxypropyltrimethoxysilane) 250 g 250 g 250 g Ethanol 60 g 60 g 60 g Si(OC2H5) 4 - - 50 g Water 25 g 25 g 30 g HNO3 0.3 g 0.3 g 0.3 g TUOC2H5) 4 100 g 100 g 100 g Water (solvent) 75 g 250 g 80 g Ethanol (solvent) 250 g 50 g 250 g y- glycidoxypropyltrimethoxysilane 300 g 300 g Ethanol 75 g 75 g Si(OC2H5) 4 75 g 75 g Water 36 g 36 g HNO3 0.5 g NH3OH 0 0.5 g 1923567 of Ti(OC3H7 ) 4 135 g 135 g HNO3 0 0.5 g Water (solvent) 75 g 450 g Ethanol (solvent) 300 g The coating is soluble in a suitable solvent depending on whether the coating has hydrophilic or hydrophobic properties. In one embodiment, the solvent is an organic solvent. In another embodiment, the solvent is a hydrophilic solvent. Non-limiting examples of a solvent are alcohol or water, optionally augmented with surfactants. In one embodiment, the solvent can be ethanol, propanol, water, or mixtures thereof, optionally including surfactants. The amount of solvent used is adjusted to suit the viscosity and / or concentration of the coating and / or the surface tension. By controlling the viscosity and / or concentration of the solution and / or the surface tension, the penetration at the vertex of surface defects can be controlled. The viscosity of the coating can also be controlled by specifically selecting (starting) components that have a desired viscosity. In one embodiment, penetration into the cracks of the glass surface, as described above, can 1923567 of 87 increase by decreasing the viscosity of the coating or coating solution The coating provided here provides a soluble organic-inorganic copolymer structure that is deposited onto the glass surface as a transparent, non-brittle film, but virtually as hard and abrasion-resistant as the glass substrate surface. In addition to the above, a positive impact on cracking in glass can be expected by preventing water vapor (typically from ambient humidity or compressed air) from being present in the atmosphere at any stage of the process, from melting and beading (or other exposure of molten glass to the atmosphere) to hot forming (such as pressing, blowing, float casting, updrafting, downdrafting, overflow melting, tube drawing, and rod drawing), up to the final coating application. Preventing the presence of water molecules on the glass surface can limit the formation of microcracks. It is considered, without adhering to any specific theory, that the presence of water vapor can promote crack propagation, as the hydroxyl groups needed for 1923567 of 87 Fill the complete valence band of the silicon atom (valence 4), which, on the surface, needs an (OH) group to complete the fourth valence. Without water vapor present, that valence cannot be filled, and, according to the theory, the crack requires significantly greater forces to propagate. It is believed that even small amounts of water present, for example in the atmosphere, trigger crack propagation, and its absence, or at least a very low concentration, can greatly limit crack propagation. The propagation of cracks through the coating is prevented, among other things, because the coating penetrates the crack to the tip of the crack to create a maximum effect. In one embodiment, the surface of the silica-containing material, including or excluding its edges, is pretreated. This pretreatment can improve coating adhesion and / or reduce the depth and / or radius of microcracks on the glass surface. The pretreatment can be carried out using any suitable (chemical) material. For example, such pretreatment can be performed with hydrofluoric acid, mechanical edge grinding, flame polishing, laser treatment, and / or any other method. 1923567 of 87 edge treatment technology, or by any other suitable methodology. By pretreating the silica-containing material, the coating can penetrate more effectively and completely into the surface of the microcracks in the silica-containing material and, in addition, can reduce any mechanical defects imposed particularly on the edges of the silica-containing material. In one embodiment, silica-containing materials (including, but not limited to, compounds) in the form of porous materials or powders, such as loose or compacted (compressed, pre-impregnated, sintered, etc.), are partially or completely soaked with the coating along the pores or within the powder lump. The soaking of the material or powder can be carried out for more than 1 second, more than 10 seconds, more than 1 minute, more than 1 hour, more than 1 day, or even more than 1 week or longer to allow for complete soaking of the voids between the pores, between the grains, or between parts of the substrate. The soaked material can then be shaped and cured, heated, further pressed, or sintered as described herein to prepare the final product. The powder or porous material can be shaped into a pre-impregnated material prior to soaking or absorption. 1923567 of 87 In one embodiment, the silica-containing material, preferably glass, is heat-treated at a suitable temperature below, around, or even above the transformation temperature Tg before applying the coating to reduce the depth, radius, or both of the microcracks on the glass surface. Suitable temperatures are at least 300 K below the transformation temperature Tg. In other embodiments, suitable temperatures below the transformation temperature Tg are at least 100 K, 125 K, 150 K, or even lower. In one embodiment, rapid cooling may be applied. Heat treatment with or without rapid cooling can allow the coating to penetrate more effectively and completely into the surface of the microcracks in the glass substrate. Furthermore, this method can allow defects (e.g., grains) within the body of the glass substrates to be homogenized or even dissolved. In one embodiment, any mechanical defect resulting from cutting or similar procedures that result in irregular edges of silica-containing materials are pre-treated before applying the coating, either by chemical etching, flame polishing, sharp edge grinding, or any other edge smoothing methodology, or any combination thereof. By using the coating provided in this document, the mechanical strength of the glass is improved compared to uncoated glass products. The increase is controllable depending on the coating used and can provide a minimum increase in mechanical strength of 50%. In one embodiment, the strength increases by more than 100%, more than 150%, more than 250%, more than 300%, more than 500%, more than 1000%, more than 1500%, more than 2000%, more than 5000%, or even more than 10000%. The strength of the glass increases by more than 0.5 times, more than 1 time, more than 1.5 times, more than 2.5 times, more than 3 times, more than 5 times, more than 10 times, more than 15 times, more than 20 times, more than 50 times, or even more than 100 times compared to the untreated genuine glass substrate. This improvement refers to the baseline mechanical strength of the untreated glass after melting, forming, and cooling.The limitation of increases in mechanical strength can only be restricted by safety concerns. As mechanical strength increases, the resulting available energy released at the breaking point will result in a more violent energy release and a greater amount of energy. 1923567 of 87 smaller glass segments or particles. The improvement in mechanical strength can be easily controlled with the present invention with an accuracy of up to 100%. The change in mechanical strength can be measured by any method known to the skilled tradesperson, such as a 3- or 4-point glass probe, a ring-on-ring probe, hydrostatic pressure with any pressure-building fluid until the device breaks, the increase in force per unit time (comparison of two different glass groups), or other methods. The effectiveness of the chemical bonding can be demonstrated by quantitative techniques such as Auger electron spectroscopy, electron probe microanalyzer (EPMA), or any other method known to the skilled tradesperson. In one embodiment, the improvement in the strength (and toughness) of the glass is between 50 and 5000%, such as between 50 and 4500%, between 50 and 4000%, between 50 and 3500%, between 50 and 3000%, or between 50% and 2500%. In another embodiment, the improvement in the strength of the glass is greater than 5000% or even greater than 10000%. The improvement in the strength of silica-containing materials can be achieved with newly manufactured silica-containing material or with damaged silica-containing material—new or used—by repairing it using the coating composition of the invention. 1923567 of 87 In addition, ductility can be increased and brittleness can be reduced. The coated glass has a strength (and toughness) of at least 150 MPa. For example, the coated glass has a strength of at least 150 MPa, 200 MPa, at least 250 MPa, at least 500 MPa, or more. In other embodiments, the strength of the glass may be at least 120 MPa, at least 100 MPa, or at least 75 MPa. The strength parameters also apply to other silica-containing materials described in this document. The increased strength of the glass, along with the increased ductility, allows coated glass to withstand high temperature differentials, such as cooling from ambient or elevated temperatures to cryogenic temperatures, or vice versa. For example, coated glass can easily withstand temperature differences of more than 50 K, 100 K, 150 K, 200 K, or even 250 K when glass from ambient temperature is frozen to very low temperatures or when glass that has been kept at sub-0 °C is thawed for a very short period. In one exemplary embodiment, vials stored at 1923567 of 87 -78 °C (195 K) or -196 °C (77 K) or -269 °C (4 K) and that are heated to room temperature in a very short period of time (such as, for example, vials for pharmaceutical vaccines) do not break, since both the strength of the glass and the ductility of the glass surface will have increased significantly with the application of the object of the invention. The refractive index of the coating can be adjusted to a desired value by adjusting the relative concentration of the metal component in the copolymer. Glass coated with the coating provided herein may have not less than 4% cloudiness after 300 cycles in the Bayer abrasion test defined by ASTM-F735. The increased strength of the glass, along with the increased ductility, can allow coated glass to withstand, or at least tolerate, greater impact forces from solid objects striking the glass at relatively high speeds and angles. In an exemplary embodiment, photovoltaic glass panels, solar thermal glass panels or tubes, or window glass would withstand hailstones or larger stones impacting at higher speeds without causing fractures or other damage. 1923567 of 87 additional exemplary realization, the coated glass would withstand higher impacts induced by violent action, such as bullets or battering rams or other impact devices hitting the coated glass. The increased strength of glass, combined with increased ductility, allows glass for containers, including but not limited to glass bottles, glass jars, drinking glasses, or any other glass with a closed or open hollow volume, to withstand significantly higher pressure from within the container or to resist significantly greater forces from any impact. In one example, bottles filled with liquids containing carbon dioxide may be prone to high or even excessive pressures, for instance, due to increased ambient temperature. Therefore, the glass bottle can be manufactured with a thinner wall at the same pressure as untreated glass or can withstand significantly higher pressures.In the same way as in the previous section

[0068] , without limiting the effect on a particular glass, a container such as a bottle, jug, or drinking glass could withstand being dropped to the ground without being damaged at all, or at least cause only minimal damage compared to a wine glass that is not. 1923567 of 87 coated with the coating that is the subject of this document, which generally breaks upon impact. Furthermore, reusable bottles (containers) can be coated with the inventive coating and can therefore be used for a much longer time in the deposit or reuse system before it becomes necessary to melt them down and form new bottles (containers). This extension in the deposit or reuse system allows for savings in energy and raw materials. The presence of additional silicon in the coating can also facilitate better bonding between the coating and the glass and may have the added advantage of reducing the refractive index for better adaptation to the glass substrate, as well as improving coating adhesion to the glass surface. This is due to the fact that silicon alkoxides retain some alkoxy bonds, even under excess water, and these bonds react with the hydroxyl bonds on the glass surface during heat treatment. Figure 2, for example, is a schematic representation of a chemical bond of the coating on a glass surface showing the covalent bonding of the coating to the glass (a) and illustrating the immobilization of sodium ions by boron coordination change. 1923567 of 87 According to the invention, one or more coatings can be applied to the glass substrate. If more than one coating is applied, the additional coatings can have different properties and can provide different or improved functionality to the glass substrate. For example, different coatings can provide different levels of strength. In one embodiment, a coating layer can provide additional oxygen sites or other bridging divalent species, such as sulfur, selenium, tellurium, polonium, copper, or ytterbium, but not limited to these, to allow for more covalent bonds for a second coating. The second or more coatings can provide additional protection against, for example, staining, weathering, and / or damage from energy release at break, or they can provide additional abrasion resistance and / or chemical resistance.With a second or subsequent coating, chemical bonds can be selectively created to ensure optimal bond uniformity by building up coatings at an Angstrom or higher level, starting from the crack tip and applying layer by layer to the surface, thus further controlling the glass's strength. In one embodiment, abrasion resistance can be enhanced with either the second or the coating. 1923567 of 87 additional. Therefore, the second or more coatings can provide (1) protection against staining, weathering and / or damage resulting from energy release at the breaking strength point, (2) improved abrasion resistance, (3) improved birefringence, (4) modification of the refractive index, (5) increased hardness, (6) protection of photovoltaic or semiconductor devices from potential-induced degradation, (7) control of the increase in mechanical strength to its design strength, with an accuracy of -50% / +100%, (8) fungicidal, antibacterial and / or antiviral properties, and / or (9) repellency of water by hydrophobicity and / or oil, grease, etc. by oleophobicity. Another important aspect concerns the application of the coating to the glass surface. For the coating to reach the crack tip, it may be desirable that no restraining force, particularly from oxygen, nitrogen, or water molecules, or argon atoms (or other species contained in the atmosphere), impede its penetration. Therefore, a controlled atmosphere using industrial or special gases such as helium, hydrogen, neon, dry air, nitrogen, argon, oxygen, ozone, carbon dioxide, or similar gases, or a vacuum, is advantageous for facilitating the coating's penetration to the crack tip. In one embodiment, the controlled atmosphere is characterized 1923567 of 87 by using helium, hydrogen, neon, oxygen, and / or ozone. In one embodiment, the controlled atmosphere is characterized by being oxygen-free. The vacuum can be an absolute pressure of up to 950 hPa, preferably below 500 hPa, more preferably below 100 hPa, and even more preferably below 10 hPa or even less. In one embodiment, the vacuum can be below 1 hPa or, if economically justified, even more preferably below 0.1 Pa, or even below 10⁻⁶ Pa, or even below 10⁻⁹ Pa. The controlled atmosphere can be applied in the application space and / or the space from the glass outlet through the hot forming device. Additionally or alternatively, heating the chemical solution just below the boiling point of the solvents and / or heating the glass substrate to a sufficiently high temperature will open the cracks, as well as reduce viscosity and increase coating penetration, allowing for better penetration and thus the repair of surface defects. Furthermore, or alternatively to the above, heating the chemical solution above its boiling point transforms it into the gaseous stage, or further energizing the chemical solution, even into the plasma stage, and / or heating the glass substrate to a sufficiently high temperature will open the cracks. Additionally, 60 1923567 of 87 to further reduce viscosity and increase coating penetration to allow better penetration and thus repair of surface defects. The coating can be applied using various methods known to those skilled in this field. For example, the coating can be applied in a liquid state (including gel), a gaseous state, or as plasma. It is also possible for the coating to be applied from solid states, most likely in the form of nanopowders. The coating can be applied using any suitable application technique employed in this technical field. In one embodiment, the coating can be applied by, but is not limited to, dip coating, spray coating, roll coating, vapor deposition (such as CVD, PECVD), misting, external plasma deposition, chemical vapor deposition, and / or plasma-induced vapor deposition (such as PICVD).The coating can also be added to a suitable solvent, such as H2O, which is used as a starting material for certain materials, such as concrete or cement, or any other material that uses a solvent or solvent mixtures. This allows for complete and uniform distribution of the coating within the material. 1923567 of 87 For example, if dip coating is applied, the withdrawal rate varies between 20 mm / min and 15,000 mm / min (250 mm / s), such as between 50 mm / min and 10,000 mm / min or between 100 mm / min and 1,000 mm / min. A faster withdrawal rate generally creates a thicker coating film, while a withdrawal rate that is too slow can result in the coating polymerizing on the surface of the glass substrate during withdrawal. Therefore, the ideal withdrawal rate depends on several factors, such as viscosity, the reaction time of the chemical compounds, etc. The typical thickness for the dip coating process is between 1 and 10 microns, such as between 3 and 7 microns. The thickness can also be (substantially) less than 1 micrometer, and the thinnest possible coating thickness is desirable. In one embodiment, the compositions a) and b) described above can be subsequently applied by any of the methods described above. In one embodiment, the compositions a) and b) can be applied by spray coating or misting using one or more different spray nozzles. In this embodiment, the coatings can be applied simultaneously or in subsequent coating stages. If a spray nozzle is used, the chemical compound 1923567 of 87 must be premixed before the nozzle inlet. If more than one spray nozzle is used, the chemical compounds may be premixed before the nozzle inlet, or the individual compositions a), b), and / or c) may be injected through separate nozzles so that the separate sprays merge before or on the surface of the glass substrate. Subsequent coating stages may also be applied through separate nozzles for each composition a), b), and / or c). If the nozzles spray the compositions separately, in addition to the individual compositions a), b), and c) through any nozzle, any premixed combination of (i) a) and b), (ii) a) and c), or (iii) b) and c) may be fed into the nozzle inlet. Any nozzle may have individual geometries that respond to the optimum spray atomization.In one embodiment, atomization can be performed under pressure without using any carrier material. In another embodiment, atomization can be performed with compressed air, or with a pressurized gas or gas mixture, for example, an inert gas such as nitrogen, but without limitation. Other atomization techniques are possible, such as molding or fittings. 1923567 of 87 mechanical or other types, electromechanical devices or plasma. The application of the coating may be supported by the use of a catalyst, such as, but not limited to, water, preferably deionized water, more preferably distilled water, or even more preferably multi-distilled water, for example, double-distilled water, to increase the reaction rate of the coating with the hydroxyl groups in the crack of the glass substrate. This catalyst may be the presence of a particular species or specific process parameters, such as temperature, pressure, plasma, or the like. It is also included in this document that the residual or unused coating, which is not necessary for the chemical reaction to create the covalent bond required for the reaction to repair some or all of the microcracks, is removed (i.e., recovered) after the coating has been applied, for example, by immersing the coated glass or rinsing the coated glass with a suitable solvent such as water and / or alcohol, so that a sufficient amount of the coating remains in the cracks to allow bonding and repair to occur effectively. The suitable solvent may 1923567 of 87 to be, but not limited to, water, ethanol, isopropanol, or mixtures thereof. In a preferred embodiment, the solvent used is ethanol. Therefore, no more coating remains than the amount required for the microcrack repair reaction, resulting in the same increase in strength, while at the same time conserving coating and also allowing the pure glass to exhibit essentially the same visual properties as when uncoated. After application, the coating is dried to remove the solvent and excess water, and then heated to promote continued condensation or precipitation polymerization of the coating and curing to a dense, glassy film. Heat treatment is carried out independently of the coating method described above. The heat treatment can be performed at a suitable temperature for a suitable period of time. For example, coated glass can be heat-treated at 100 to 500 °C, such as 100 to 400 °C, 100 to 300 °C, or 100 to 200 °C for 30 minutes, 60 minutes, 2 hours, or even longer than 2 hours, but this is not a limitation. Processing temperatures above 150 °C and even above 200 °C can result in shorter treatment and / or curing times, which are generally preferred. The drying stage can also be supported. 1923567 of 87 by the use of a vacuum of an absolute pressure of 950 hPa, preferably below 500 hPa, more preferably below 100 hPa, even more preferably below 10 hPa or even less. After the coating is applied, it cures. In one embodiment, the curing of the applied coating takes place at temperatures above 30°C, such as above 50°C, above 80°C, above 100°C, above 120°C, above 130°C, above 150°C, above 200°C, or even above 300°C. The curing temperature is applied for a sufficient period of time to achieve curing. For example, curing may take place over a period of time lasting milliseconds, such as at least 100 ms, 200 ms or more; seconds, such as at least 10 s, 30 s, 45 s or more; or even minutes, such as at least 1 min, 2 min, 3 min, 5 min, 10 min, 20 min, 30 min, or even more. In another embodiment, curing is activated by exposing the coated silica-containing material, preferably glass, to specific waves of suitable frequencies and / or wavelengths. Non-limiting examples of suitable wavelength / radiation ranges include, for instance, ultrasonic, such as subsonic, sonic, or supersonic. 1923567 of 87 visible range, ultraviolet range, extreme ultraviolet range, infrared range, microwave range, or any other distinct range that responds to particular correlated wavelengths that cause molecules to react (e.g., the individual natural frequency of the reactive group molecule). In another embodiment, the coated silica-containing material is exposed to tempering before or after coating. In one embodiment of the method of the present invention, composition a) and composition b) or composition a) and the mixture of composition b) and composition c) can be applied sequentially to the glass surface and also cured sequentially. In some hot forming processes, it might be possible to create a controlled atmosphere or a vacuum of an absolute pressure of up to 950 hPa or less with very little or no water vapor content, for example, air conditioning with a dew point below -20 °C (253 K), more preferably below -50 °C (223 K), more preferably below -78.5 °C (194.7 K), if economically justifiable even more preferably below -195.8 °C (77.35 K), more preferably below -246 °C (27 K), more preferably at -269 °C 1923567 of 87 (4 K) from the outlet of the molten glass to any part of the forming device or even through an annealing furnace, thus preventing, as far as possible, the water from reacting with the glass surface and thereby improving the outcome of the chemical reaction with the glass surface. In addition, the absence or significant reduction of the presence of water vapor can prevent crack propagation during the crack formation process and, therefore, less coating material may be required since the crack depth and its resulting volume may be smaller and the resistance to coating penetration into the resulting crack voids may be greatly reduced. With the present invention, any of the process stages from batch storage, batch mixing, batch loading, if applicable, batch preheating, melting, refining, droplet forming, hot forming, etc., up to the application of the coating, or even all or parts of the entire process, from batch storage to the application of the coating, can optionally take place in a controlled atmosphere (as 1923567 of 87 described above) with a very low water vapor pressure (partial pressure of water vapor). The use of the coating will benefit all glass applications and products. For example, but not limited to, the coating can be applied to containers for beverages, spirits, food, and pharmaceuticals; flat glass (e.g., automotive, architectural, photovoltaic, and thermal solar); and electronic devices (e.g., computer displays, laptop screens, smartphones, and wafer-level encapsulation).mirrors or mirror substrates, aerospace applications, astronomy applications, ophthalmic devices, optical devices, optical fibers or other communication fibers, reinforcing textile fibers, insulating fibers, glass tubes and / or rods (e.g., for pharmaceutical packaging, solar thermal, photovoltaic solar, lighting tubes), blank masks (for microlithography), glass, ceramic, glass-ceramic or composite membranes (e.g., for batteries, fuel cells), pressed glass for, e.g., high-precision reflectors, LED or OLED applications, powdered glass, as protection against leaching or for vitrification glasses of; 1923567 of 87 wastes (e.g., ash vitrification, nuclear waste vitrification). The invention is not limited to a specific type of glass, but can be applied to any glass and for any purpose. Suitable types of glass may include, but are not limited to, soda lime, borosilicate, aluminosilicates, opal glass, sapphire, calcium fluoride, chalcogenite glasses, silica (pure or doped), glass-ceramics, ceramics, pure or impure quartz, glass or quartz crystals, composite materials consisting of any type of glass or ceramic or glass-ceramic and at least one other material, or the like. For example, the coating can be applied to all glasses that melt at high temperatures of at least 450°C, at temperatures above 1100 °C, or temperatures above 1400 °C. Generally, there is no upper temperature limit; that is, the coating can be applied to any molten or shaped glass once a suitable application temperature is reached, i.e., without the coating decomposing. Therefore, the coating can be applied, for example, and provided that no decomposition of the coating material occurs, to all glass manufactured or shaped at or around the transition temperature (Tg) + / - 300 °C, or to all the 1923567 of 87 glass produced by applying the sol-gel process at temperatures below 1200 °C, below 1000 °C, below 850 °C, below 600 °C, below 450 °C, below 300 °C, or even below 150 °C, said coating being applied upon reaching a suitable temperature. In one embodiment, the coating can be applied at temperatures below 450 °C. In one embodiment, the coating of the invention is not applied to polymeric substrates. In one embodiment, the coating of the invention is not applied to polycarbonates. In one embodiment, the coating of the invention is not applied to acrylates. The invention is also suitable for all possible preparation processes, such as, among others, any hot forming technology, in particular, but not limited to, press blowing (e.g., on single-section machines, NNPB (narrow neck pressure blowing), blow-blowing process, float glass, laminated flat glass, tube forming (e.g., tube drawing by the Danner process, Vello process, etc.), pressing, updrafting, downdrafting, overflow melting, pressing, blowing, casting, carousel-type machines, tube-to-container conversion; any cooling device or 1923567 of 87 temperature heating to control the temperature of the glass and the distribution of the temperature of the glass. In one embodiment, prior to the application of the coating, the molten glass is stretched immediately after a hot forming process to create thinner glass and / or to reduce glass defects. In an additional aspect, the present invention relates to a product containing glass or silica that has a coating as described herein. The coating on the glass product can have a thickness suitable for its intended purpose. For example, the coating can be less than 10 microns thick. In one embodiment, the coating can be less than 5 microns thick, such as less than 3 microns, less than 2 microns, or even less than 1 micron. Even thinner coatings can be applied. The coating can be controlled in various ways, such as by the viscosity and / or concentration of the coating solution and / or the surface tension, the duration of application of the coating to the glass, the temperature, atmospheric control, ambient pressure, or a vacuum from an absolute pressure as defined above, and the like. In general, lower viscosity leads to greater effectiveness of the coating fluid. 1923567 of 87 coating to penetrate into the microcracks, resulting in more reactants reacting and thus creating more covalent bonds. In general, it is beneficial to provide the coating as thin as possible. In an additional aspect, the present invention is directed to a coating prepared by a method provided in this document. In another aspect, the present invention is directed to a coating comprising a mixture of a) a composition comprising 50-85 wt% of one or more alkoxysilane(s) of general formula RxSi(OR1)4-x with up to 35 wt% of one or more metal or metalloid oxide(s) and / or one or more metal or metalloid alkoxide(s) in the presence of up to 10 wt% of water and up to 30 wt% of an alcohol and up to 1 wt% of a catalyst, wherein R is an organic radical, R1 is independently selected from hydrogen and C1-18 alkyl, or isomers or polyvalences thereof, and x is an integer from 0 to 3; b) a composition comprising 20-100% by weight of one or more metal or metalloid oxide(s) and / or one or more alkoxide(s) of 1923567 of 87 metal or metalloid, up to 80% by weight of an alcohol, up to 20% by weight of water and up to 1% by weight of a catalyst; and c) a composition comprising up to 50% by weight of one or more metal or metalloid oxide(s) and / or one or more metal or metalloid alkoxide(s), up to 100% by weight of water and up to 100% by weight of an alcohol; where the weight percentage of a), b), c) and the mixture of the same, respectively, adds up to 100% by weight. In this aspect of the invention, the information and specific embodiments provided above also apply. In another aspect, the present invention relates to a method for improving the (mechanical) strength of glass, comprising applying one or more coatings, as provided herein, to the glass. The one or more coatings are applied as described above. The method may further comprise the step of preparing one or more coatings, as provided herein. All the above embodiments can be combined in any way possible. The embodiments specifically addressed to glass also apply to the other silica-containing materials described herein. 1923567 of 87 EXAMPLES To describe the present invention in more detail and to aid in understanding the present description, the following non-limiting examples are provided to fully illustrate the scope of the description and should not be construed as specifically limiting its scope. EXAMPLE I A transparent, hard, and non-brittle coating solution is prepared as follows: 100 grams of glycidoxypropyltrimethoxysilane, O / \ (CH^HCHiOtCH^jSiíOCHj)^ is mixed with 100 grams of ethyl alcohol, C2H5OH. To this mixture, 8 grams of water and 0.3 grams of nitric acid, HNO3, are added, and the mixture is stirred for 10 minutes. This procedure hydrolyzes the methoxy groups of the compound, converting them into hydroxyl groups. After this, 40 grams of titanium ethoxide, Ti(OC2H5)4, are also added, and the mixture is stirred for another 10 minutes to react with the hydroxyl bonds, chemically linking the titanium compounds to the molecular structure of glycidoxypropylsilane through the oxygen. Once the titanium and the organic component are chemically linked by this procedure, additional water can be added without fear of causing condensation. 1923567 of 87 or segregated precipitation. This water causes greater polymerization of the system into long chains and leads to coating hardness by removing excess organic matter from the structure. Several 10 cm x 10 cm, 2 mm thick float glass samples were coated by immersion in this solution and heat-treated for 30 minutes at 130°C. Their abrasion resistance was tested using the ASTM F-735 Bayer abrasion test method for 300 cycles and found to be approximately 1.0, which is virtually the same as the abrasion resistance of the uncoated glass surface. The strengths of these samples were also measured using the standard ring-on-ring method and the cone cracking load method at Penn State University. The results are shown in Fig. 3.Uncoated glass showed the typical bell-shaped strength distribution between 50 and 150 MPa, with an average value of approximately 100 MPa. In contrast, the coated samples showed a strength distribution in the range of approximately 200 to 350 MPa, with an average strength of approximately 250 MPa, representing a 2.5-fold increase in strength. Figure 4 compares the average and range of the mean cone cracking load. 1923567 of 87 of the glass samples. It can be seen that the tin side of the glass (i.e., the underside of the float glass in contact with the tin bath on which the glass floats) has significantly lower crack resistance than the air side (i.e., the top side of the float glass) due to microscopic defects caused by the aforementioned and other phenomena. More significant are defects in the surface support steel rollers through which the glass is pulled after leaving the tin bath. These rollers can create scratches on the underside of the glass. Some of the defects in the steel rollers may be due to glass fragments from the cutting process. EXAMPLE II A non-brittle, abrasion-resistant coating solution was prepared as in Example I, except that titanium isopropoxide, Ti(OC3H7)4, was used instead of titanium ethoxide. The abrasion resistance and toughness results were virtually identical. EXAMPLE III. Several coating solutions were prepared as in Example I, except that zirconium and aluminum alkoxides, Zr(OC3H7)4 and Al(OC4H9)3, were used instead of titanium ethoxide Ti(OC2H5)4. 1923567 of 87 EXAMPLE IV 100 grams of glycidoxypropyltrimethoxysilane are mixed with 100 grams of ethyl alcohol, C2H5OH. To this mixture, 8 grams of water and 0.3 grams of nitric acid are added, and the mixture is stirred for 10 minutes. Then, 40 grams of titanium isopropoxide, Ti(OCsH7)4, and 5 grams of silicon ethoxide, Si(OC2H5)4, are added, and the mixture is stirred for another 10 minutes, polymerizing them with the glycidoxypropyltrimethoxysilane. Once this is done, 150 grams of water and 30 grams of ethanol are added to further polymerize the structure to a higher molecular size, as well as to remove most of the terminal organic bonds from the structure. This solution was also applied to glass samples, and its strength and abrasion resistance were tested. Similar results were obtained, as shown in Example I. EXAMPLE V The coating solution was prepared as in Example IV, except that silicon was introduced from 3 grams of silicon methoxide, Si(OCH3)4. The results were similar to those provided in Example IV. To investigate the effect of the coating on the strength of the glass as a function of the thickness of the glass, a solution was prepared as in Example IV and coated 78 1923567 of 87 on samples of float glass that had various thicknesses. As the glass becomes thinner, the effectiveness of the coating increases. The coating increased the average strength of the glass from 130 MPa to ~250 MPa when the thickness was 3 mm, but increased to over 300 MPa when the thickness was 2 mm. EXAMPLE VI The coating solution is prepared as in Example IV, except that 3 grams of silicon methoxide, Si(OCHs)4, were used instead of silicon ethoxide, Si(OC2Hs)4. The results were similar to those provided in Example IV. EXAMPLE VII The coating solution is prepared as in the Example IV, except that 4 grams of methyltrimethoxysilane, CH3Si(OCH3)3, are added instead of silicon methoxide, along with titanium isopropoxide. The resulting coating on the glass not only strengthened it similarly but also made it hydrophobic, thus providing an additional property and protection against staining and water-related chemical effects. EXAMPLE VIII The coating solution is prepared as in Example IV, except that instead of silicon ethoxide, it is 1923567 of 87 added 2 grams of dimethyl methoxychlorosilane, (CH3)2Si(OCH3)Cl, along with titanium isopropoxide, Ti(OC3H7)4. The resulting coating not only strengthened the glass but was also hydrophobic. EXAMPLE IX The coating solution was prepared as in Example IV. Hydrophobicity was introduced by adding 2 grams of a commercially available fluorine compound to the solution. The results for increased strength were similar to those in Examples I and IV, except that the coating had the additional property of being both hydrophobic and oleophobic. EXAMPLE X The following Tables 1 and 2 provide further experimental evidence that the use of the coating as provided herein (all coated examples are within the inventive coating) leads to an improvement in the strength of the glass. Table 1: Resistance - 2 mm glass [MPa] Sample # Uncoated Coated Difference 2-1 157 1923567 of 87 2-2 159 2-3 ​​266 2-4 178 2-5 79 2-6 262 2-7 301 2-8 364 2-9 292 2-10 314 Averages 167.8 306.6 82.7% Table 2: Strength - 3 mm glass [MPa] Sample # Uncoated Coated Difference 3-1 128 3-2 106 3-3 110 3-4 136 3-5 171 3-6 213 3-7 227 3-8 283 3-9 311 1923567 of 87 3-10 246 Averages 130.2 256 96.6% EXAMPLE XI Figures 5a and 5b show an example of glass reinforcement according to the present invention. The uncoated sample (Fig. 5a) exhibits a relatively moderate fracture pattern, which is evidence of the relatively low energy required for destruction. Here, a low force of approximately 79 MPa (approximately 11,600 psi) created the fracture pattern. In contrast, the coated sample (Fig. 5b) exhibits a relatively significant fracture pattern, which is evidence of the relatively higher impact required for destruction and, therefore, for the improved mechanical strength of the glass. Here, a higher force of approximately 364 MPa (approximately 53,000 psi) was required. The surface coating was approximately 2.4 microns thick. EXAMPLE XII Figure 6 shows a dealkalization analysis of (sodium) coated and uncoated glass whereby the coating takes a silica hydroxyl bond terminated with -Si-OH, and after the reaction now links oxygen with boron -OBO- instead of, for example, -O-Si-O-. The graphs show cumulative sodium leaching from samples of 1923567 of 87 clear float glass 4.5 x 4.5 immersed in 250cc of H2O at 60 °C (140 °F). As can be seen in the graphs, essentially no sodium leaches off the modified (coated) surface, unlike uncoated glass. EXAMPLE XIII A glass surface mechanically damaged using the Vickers impression method with 10–20 N results in severe surface damage (Figure 8 shows a soda-lime float glass probe, intentionally mechanically damaged with a Vickers impression, under different illumination conditions using a microscope). A coating solution of the present invention is then applied to the glass surface. The coating cures in less than 60 minutes at temperatures above 30°C. Figure 9 shows a sample of soda-lime and borosilicate glass with the Vickers impression without coating on the left and a coated soda-lime glass sample after Vickers impression on the right, along with the average break test results. Figure 10 illustrates a detailed analysis of the surface structure of the Vickers impression.The top view shows the morphology of the Vickers print in a digital three-dimensional image. 1923567 of 87 computer-animated digital microscope image. In the center-left portion, a vertical plane signifies the analyzed plane in which the Vickers indentation angle was measured, as shown below (here: the vertical and horizontal scales are different). The Vickers indentation angle is 148.26° and the Vickers indentation depth is 11.67 pm. The center-right portion is the same image as the lower-right image in Figure 8. As can be seen in Figure 9, the previous damage is not visible to the naked eye, and even under a microscope, it is barely perceptible. Furthermore, the mechanical strength of the glass returns to the level of the original undamaged glass values, less than 10% lower than the original uncoated, undamaged glass, and in some cases, even higher compared to the original undamaged glass. Figure 11 describes the detailed values ​​for the break tests (1) for uncoated glass without mechanically induced defects, (2) for uncoated glass with mechanically induced defects (partially treated at different temperatures), and (3) for glass samples with mechanically induced defects that have been coated after the defects were applied (coating solution 1: glycidoxypropyltrimethoxysilane, 1923567 of 87 EtOH, H2O, Ti(OC2H5)4; coating solution 2: glycidoxypropyltrimethoxysilane, EtOH, Si(OCH3)4,H2O, Ti(OC2H5)4; coating solution3: glycidoxypropyltrimethoxysilane, EtOH, B(OCH3)3,H2O, Ti(OC2H5)4; all in the quantities described herein) and exposed to different temperatures. As can be seen in Figure 11, the process for curing mechanically induced surface defects was as follows: (1) A set of undamaged samples was analyzed for mechanical breakage. (2) A set of samples was pre-damaged with a Vickers indentation but not coated, then kept at room temperature or subjected to heat treatment for 30 minutes at 120 °C. 135°C or 150°C before exposure to the mechanical breaking test. (3) All other samples were pre-damaged with a Vickers impression and then coated with different solutions (recipes) before exposure to the mechanical breaking test. Tables 1 to 3 in the accompanying file show the general recipes for solutions (recipes) 1, 2, and 3 used in the test. After mixing any of solutions 1 to 3, the samples were exposed to curing temperatures of 120, 135, or 150°C, as indicated. For solutions 2 and 3 and for 135°C, the 1923567 of 87 solution was coated with the glass substrate 2 hours after mixing the solutions. Having described the nature of the present invention and the manner of putting it into practice, it is hereby declared that what is claimed as the invention and exclusive property is: -------- CLAIMS CONTINUE ON PAGE 1 ------86 1923567 of 87 MUCHALL SRL - 30679678961 Digitally signed by PORTALTRAM ITES - INPI Date: 2022.08.17 15:00:36 -03:00 Reason: Digitally Signed by the INPI Location: Buenos Aires, Argentina 1923567

Claims

1. A method for preparing coatings to improve the strength and fracture toughness of glass, characterized in that the method comprises mixing a) a composition comprising 50-85 wt% of one or more alkoxysilane(s) of general formula RxSi(OR1)4-x with up to 35 wt% of one or more metal oxide(s) or metalolide and / or one or more metal or metalloid alkoxide(s) in the presence of up to 10 wt% of water and up to 30 wt% of an alcohol and up to 1 wt% of a catalyst, wherein R is an organic radical, R1 is independently selected from hydrogen and C1-18 alkyl, or isomers or polyvalences thereof, and x is an integer from 0 to 3, wherein the reaction is carried out until no free water remains in the solution for the next step; wherein the alkoxysilane is partially hydrolyzed;and where one or more metal or metalloid alkoxides are selected from alkoxides of boron, aluminum, gallium, indium, thallium, germanium, tin, lead, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, copper, silver, gold, palladium, platinum, zinc, cobalt, rhodium, iridium, selenium, tellurium, polonium. b) a composition comprising 20-100% by weight of one or more metal or metalloid oxide(s) and / or one or more metal or metalloid alkoxide(s), up to 80% by weight of an alcohol, up to 20% by weight of water, and up to 1% by weight of catalyst; and c) a composition comprising up to 50% by weight of one or more metal or metalloid oxide(s) and / or one or more metal or metalloid alkoxide(s), up to 100% by weight of water and up to 100% by weight of an alcohol; wherein compositions a), b) and c) are prepared sequentially in any order;wherein the compositions are used in a proportion of 20-70% by weight of composition a), 5-40% by weight of composition b), and 10-50% by weight of composition c); wherein the weight percent of each of compositions a), b), and c), respectively, sums to 100% by weight; wherein one or more metal or metalloid oxide(s) is not a ceroxide; and wherein alkyl, heteroalkyl, alkoxy, or alkene groups having fewer than 18 carbon atoms are used. Nine claims follow;