EP2057101A1

EP2057101A1 - Strengthening glass using coatings

Info

Publication number: EP2057101A1
Application number: EP07734855A
Authority: EP
Inventors: Serge Guy Marsaud; Katrin Wondraczek
Original assignee: Corning Inc
Current assignee: Corning Inc
Priority date: 2007-02-28
Filing date: 2007-02-28
Publication date: 2009-05-13
Also published as: TWI472497B; JP2010520138A; CN101641302A; JP5709379B2; CN101641302B; TW200906754A; WO2008104825A1

Abstract

Compositions and methods of creating and applying coatings for strengthening glass substrates are made from precursors and additives that use an under-stoichiometric amount of water, for example, wherein a ratio of water in said additive to said precursor is equal or less than about 0.5 moles of water per mole alkoxy group in the precursor.

Description

STRENGTHENING GLASS USING COATINGS

BACKGROUND OF THE INVENTION

1. Field of the Invention

[0001] The present invention is directed to compositions and methods of creating and applying coatings to glass substrates for strengthening same.

2. Description of Related Art

[0002] Glass is very sensitive to mechanical stress. Theoretically, regarding its structure, glass should have a very high strength. However in practice, devices fabricated from glass exhibit lower strength and higher failure rates than predicted due to mechanical imperfections, essentially surface defects. Thus, failure rates are determined at least in significant part by the quality of the glass at the surface and edges. Unfortunately, these types of defects contribute to reducing the useful lifetime of the glass.

[0003] Those skilled in the art have long sought a means for alleviating the problems associated with low glass strength. However, some of the discovered modifications and application processes have had undesirable side-effects, and in some cases contributed to a reduction in reliability of glass strength. In some cases, the procedures for • handling the glass during substrate manufacture and/or intended strengthening procedures create additional defects in the glass surface and edges, thereby reducing strength. For instance, fusion drawn glass sheets usually have a pristine surface quality; however, subsequent steps during fabrication are likely to create micro defects, thereby drastically decreasing the strength of the glass. As a result, skilled artisans have focused on reducing these defects in the glass substrate subsequent to flaw creation.

[0004] Possibilities for strengthening the glass after flaw creation include thermal tempering and chemical tempering. Chemical tempering requires an ion exchange involving generally alkaline elements over a penetration depth of about 10 μm, which strengthens the glass by induced compression at the surface. However, in the case of alkaline-free glass, such as EAGLE™ glass (from Corning Incorporated), chemical tempering is not a possibility due to the lack of exchangeable ions. Further, thermal or chemical tempering does not assure the long term performance of the glass, and such processes can be expensive to implement.

[0005] For long term strengthening and protection of the glass surface, the application of coatings may be a very effective process for treating defects, partially curing or at least minimizing their consequences on the glass as shown in H. Scholze. Glas, Natur, Struktur und Eigenschaften. Springer Verlag, Berlin, Heidelberg 1977. Chapter: 3.5 "Mechanische Eigenschaften" . From the existing literature, there are at least two general types of coatings used for such glass strengthening: sol-gel based hybrid coatings and polymeric coatings . It is believed that a careful choice of processing parameters during melting, drawing and finishing should avoid the formation of defects in the surface of the glass. It is believed that elimination of defects may be achieved via fire polishing, HF etching, or alkaline etching (preferably for silica glasses) . When utilizing HF etching to eliminate the surface defects, special formulations have to be used in order to avoid an increase in surface roughness, which would also contribute to a decrease in strength.

[0005] The mechanism of strengthening glass using coatings has been discussed at length in the scientific community. So far, water protection and the introduction of closure stresses within the cracks are among the accepted reasons as to why coatings are believed to strengthen glass. Other reasons, which may be of uncertain importance, are the existence of thermal compressive stresses in the glass, thermal expansion mismatch stresses in the coating, and crack shortening (coating penetration) as shown in R. J. Hand, B. Ellis, B. R. Whittle, F. H. Wang. J Non-Cryst Sol, 2003, 315, 276-287, Epoxy based coatings on glass strengthening mechanisms, and in B.D. Fabes G. D. Berry J. Non-cryst. Sol. 1990, 121,357-364, Infiltration of glass flaws by alkoxide coatings. For example, strengthening can occur when the coating has a lower coefficient of thermal expansion ("CTE") than the glass substrate because a significant CTE mismatch between coating and substrate results in compressive stress on the substrate surface as shown in L. Nikolie, L. Radonjic. Ceram Internat. 1998, 24, 547-552. Effect of the silica sol-gel coatings on the properties of glass substrate.

[0006] Validation of any improvement in the failure characteristics of the coated glass requires a demonstrable improvement in both parameters of the Weibull failure distribution curve: Weibull modulus and failure strength. The Weibull modulus is an indication of whether the defects in a glass sample are distributed uniformly throughout the tested region of the glass. Failure strength increases that have been reported in the literature range from about 30% up to almost 300%. The highest failure strength increase has been achieved using a coating system including epoxy resin, hardener and silane. However, achieving high failure strength does not guarantee a high Weibull modulus - and both a high Weibull modulus and high failure strength are desired for maximizing the overall reliability of the glass .

[0007] Therefore, there is a need in the art for coating compositions and application processes that do not lower or otherwise severely inhibit improvements in both the Weibull modulus and the failure strength.

SXJMMARY OF THE INVENTION

[0008] In accordance with one or more embodiments of the invention, compositions and methods relating to the creation and application of coatings for strengthening glass substrates that already have surface flaws (or with non-defect free glass surfaces) include applying a thin film of a composition, made from a sol-gel precursor that is pre-hydrolyzed with an additive comprising at least water, to a glass substrate. Application of the composition may occur at ambient conditions, and the glass substrate with the composition coating layer is cured at moderately elevated temperatures . The moderately elevated temperatures used allow the potential for organic groups to still be present after thermal treatment. The coating might be bonded chemically to the glass substrate. Other curing conditions may be used; for example, a skilled artisan may use UV curing or local curing on the edges in addition to thermal curing. Additionally, coatings according to various embodiments of the present invention may be applied in any way known in the art, such as dip coating. Further, the coating methods may call for application of the composition to any portion of the glass substrate.

[0009] According to one or more aspects of the present invention, a composition for a glass substrate coating may include a precursor and an additive, which contains an under-stoichiometric amount of water. The amount of water in the additive allows hydrolysis to occur when mixed with the precursor, and in some embodiments, the only water necessary for hydrolysis may be obtained from the humidity of ambient air. The precursor provides the foundation for the coating composition, and may contain Si, Ti, cross linkable moieties, or any combination thereof. Once a precursor and additive react to form a composition, the composition may be diluted with a solvent, such as water or alkanol, i.e., ethanol or isopropanol, to adjust the viscosity of the composition. It is noted that water can be used as solvent as well, which may yield even better results than, for example, using ethanol to dilute poly(3-aminopropyl) silsesquioxane. Also, additional coating compositions may be created through mixing a composition with another composition when necessary.

[0010] The advantages of this invention are best understood after reading the detailed technical description, and in relation to existing glass substrate coating processes and compositions. Nonetheless, some of the advantages are highlighted below.

[0011] The coatings in the present invention use an under stoichiometric amount of water, which yields a reaction product with a differently condensed molecular structure (as compared with the prior art) . The approach effectively hinders crack propagation when used to form/apply the coating. Whereas the conventional coating compositions are created in a stoichiometrical excess of water, there is very limited presence of water in the present invention, and such low-water containing compositions yield an improved, if not maximized, Weibull modulus and failure strength combination that has not previously been achieved with other coatings and processes.

[0012] Using silsesquioxanes (1 mol of, for example, γ- aminopropyl triethoxy silane or glycidoxypropyl trimethoxy silane pre-hydroIyzed with 1.5 mol of water) for strengthening

(increasing Weibull modulus and failure strength) pre-damaged glass has not previously been employed. Moreover, the use of cross-linkable silsesquioxanes allows for further cross-linking of the organic moieties, yielding a more dense network without precipitation, as is usually observed when working with an excess of water for hydrolysis.

[0013] In addition, the hybrid organic-inorganic functionalities of the coating compositions cured around 200 degrees C not only reinforce the glass substrate but also have the potential to protect the surface from mechanical impacts . Fully pyrolyzed inorganic coatings yield a strength increase but no protection from mechanical impacts, which would be directly transmitted from the coating to the brittle substrate material.

[0014] Other aspects, features, advantages, etc. will become apparent to one skilled in the art when the description of the invention herein is taken in conjunction with the accompanying drawings . BRIEF DESCRIPTION OF THE DRAWINGS

[0015] For the purposes of illustrating the various aspects of the invention, wherein like numerals indicate like elements, there are shown in the drawings simplified forms that may be employed, it being understood, however, that the invention is not limited by or to the precise arrangements and instrumentalities shown, but rather only by the issued claims. The drawings may not be to scale, and the aspects of the drawings may not be to scale relative to each other. To assist those of ordinary skill in the relevant art in making and using the subject matter hereof, reference is made to the appended drawings and figures, wherein:

[0016] FIG. 1 is a graph depicting the change in Weibull parameter and failure strength of the strength distribution of coated specimens versus that of uncoated specimens using a number of types of sample substrates according to the prior art.

[0017] FIG. 2 is a drawing illustrating a coating composition applied to one surface of a glass substrate.

[0018] FIG. 3 is a drawing illustrating a coating layer covering most or all of the surfaces of a glass substrate.

[0019] FIG. 4 is a graph depicting the Weibull modulus and the failure strength increase potential for a prior art coating and for a new coating composition according to one or more aspects of the present invention.

[0020] FIG. 5 is a table listing the precursors, additive (s), solvents, dip coating withdrawal speeds, and curing temperatures for coating compositions according to one or more embodiments of the present invention. [0021] FIG. 6 is a table listing changes in Weibull modulus and failure strength for a number of coating compositions and processes used on Coming's EAGLE™ glass substrates according to various aspects of the present invention.

[0022] FIG. 7 is a table listing changes in Weibull modulus and failure strength for a number of coating compositions and processes used on Coming's EAGLE™ glass substrates according to the prior art.

DETAILED DESCRIPTION OF THE PRESENT INVENTION

[0023] The invention includes compositions and methods relating to the creation and application of coatings for strengthening of pre-damaged glass substrates. In particular, the present invention relates to compositions and methods for creation and application of coatings onto thin and ultra-thin glass , such as Corning Incorporated EAGLE™ glass .

[0024] FIG. 1 is a chart showing changes in the Weibull modulus and changes in the failure strength resulting from coating a number of (different) glass substrates. All five coating/substrate combinations of FIG. 1 are in accordance with the prior art. While there is always an increase in the strength of the coated glass specimens versus that of uncoated glass specimens, there is also a resultant decrease in the Weibull parameter due to the coating. Thus, there is a decrease in the overall strength distribution of the glass. The coatings used in the experiments from which the data of FIG. 1 was taken were applied from aqueous solutions. The water employed for hydrolysis of the precursor in the three coatings/substrates on the left of FIG. 1 was used in a stoichiometric excess process . Even in cases where the Weibull parameter of the glass specimens does not fall as a result of the coating process, the net increase in the Weibull modulus and the failure strength does not achieve satisfactory levels.

[0025] According to one or more embodiments of the present invention, a composition for a glass substrate coating may include a precursor and an additive, which contains an under-stoichiometric amount of water. The additive provides an amount of water for allowing hydrolysis to occur when mixed with the precursor. In an embodiment of the invention, the only water necessary for hydrolysis may be obtained from the humidity of ambient air.

[0026] The precursor provides the foundation for the coating composition and may contain Si, Ti, cross linkable moieties, or any combination thereof. In one or more embodiments, a precursor is mixed with an additive. Many mixing methods known to those of skill in the art may be used. For example, the composition may be mixed in a PE bottle with a cap by stirring the precursor and additives together. After mixing a precursor with the additive(s), an adequate amount of time is needed for the reaction to form a composition. Once the reaction is complete, the composition may be diluted with a solvent to adjust the viscosity of the composition. In one or more embodiments, the solvent may comprise at least one of: an organic solvent containing one or more hydroxyl groups, ethanol, isopropanol, glycol, ethylene glycol, and water. Also, in one or more embodiments of the present invention, a previously created composition may act as a precursor or an additive for the creation of additional coating compositions through mixing one composition with another composition.

[0027] Referring to FIG. 2, a glass substrate 100 is illustrated with a coating layer 112 in accordance with one or more embodiments of the present invention. The coating layer 112 is depicted on one surface of the glass substrate 100; however, the coating layer 112 may cover a greater amount of the glass substrate surface. For instance, referring to FIG. 3, the coating layer 112 covers some or all of the surfaces of the glass substrate 100. It is noted that the term "surface" as used herein has a definition broad enough to cover the major surfaces of the substrate and/or the edges thereof. The coating layer 112 may be applied with dip coating or any other method of application known in the art. Although the specific parameters of the dip coating process may vary depending on the composition of the solvent, the dilution characteristics, etc., one example of a withdrawal speed is between about 5 cm/minute to about 10 cm/minute.

[0028] Once the glass substrate 100 with the applied coating layer 112 is withdrawn from the coating composition, the glass substrate 100 with the applied coating layer 112 may be cured. Curing may occur with thermal curing, UV curing, local curing on the edges, or other curing conditions known to a person of skill in the art. In one or more embodiments of the present invention, the coating layer may end up with a thickness between about 5 nm and about 500 nm after thermal treatment. In one or more embodiments, the moderately elevated curing temperature may be in the range of about 80 degrees Celsius to about 500 degrees Celsius. Process temperature, viscosity of the coating composition, and final coating thickness may be adjusted to coincide with the glass substrate type used.

[0029] Reference is now made to FIG. 4, which is a graph depicting the Weibull modulus and the failure strength increase potential for a prior art coating and for a coating composition according to one or more aspects of the present invention. Although the prior art coating and process as demonstrated on EAGLE™ glass substrates resulted in an increase in both the Weibull modulus and the failure strength (as contrasted with the selection of examples shown in FIG. 1 which use other glass substrates than the display glass EAGLE™) , such increases were moderate at best and unsatisfactory. According to the coating and process of one or more embodiments of the present invention, however, significant increases in both the Weibull modulus and the failure strength of the coated glass are achieved. The specific coating (poly (3-glycidoxypropyl) silsesquioxane- poly(3-aminopropyl) silsesquioxane 3:1) for which the illustrated results correspond will be discussed in more detail later herein.

[0030] In a general aspect, a composition for a glass substrate coating includes the precursor and an additive, where a ratio of water in the additive to the precursor is maintained at an under- stoichiometric amount . This is maintained by introducing or controlling the amount of water as a function of the number of alkoxy groups in the precursor. The precursor may contain between 1 and 4 alkoxy groups . It has been discovered that desirable strength results are obtained when the amount of water is controlled such that there is less than about 0.5 moles of water per mol of precursor per alkoxy group. Controlling the amount of water such that there is less than about 0.17 to about 0.5 moles of water per mol of precursor per alkoxy group is believed to be acceptable. Other contemplated ranges include: (i) less than about 0.33 to about 0.5 moles of water per mol of precursor per alkoxy group; and (ii) less than about 0.33 moles of water per mol of precursor per alkoxy group . [0031] Thus, on one extreme, if there is 1 alkoxy group in the precursor, the water is maintained at less than about 0.5 moles of water per mole of the precursor. If there are 2 alkoxy groups in the precursor, the water is maintained at less than about 1.0 moles of water per mole of the precursor. If there are 3 alkoxy groups in the precursor, the water is maintained at less than about 1.5 moles of water per mole of the precursor. On the other extreme, if there are 4 alkoxy groups in the precursor, the water is maintained at less than about 2.0 moles of water per mole of the precursor.

[0032] Reference will now be made to FIG. 5, which is a table listing the precursors, additive (s), solvents, withdrawal speeds, and curing temperatures for coating compositions according to one or more embodiments of the present invention. Details regarding these embodiments of the invention are provided below.

[0033] In one or more embodiments, a coating agent may be created via a reaction between a precursor and water. By way of example, the precursor may be any aminosilane or any epoxysilane, - for example (3-aminopropyl) triethoxysilane

("GAPS"), or (3-glycidoxypropyl) trimethoxysilane ("GLYMO"), which yields a poly (3-aminopropyl) silsesquioxane or polyglycidoxypropyl-silsesquioxane, respectively; any other silsesquioxane; or a combination thereof. Alternatively, the coating agent may be created via a reaction between a precursor and water plus a catalyst. Still further, the coating agent may be created via a reaction between a precursor and water plus a chelating agent, such as when titanium alkoxides are used. Still further, the coating agent may be created via a reaction between a precursor and water plus a catalyst and a chelating agent, such as when it is desirable to employ an in- situ combination of Si-alkoxides and/or Ti-alkoxides . It is noted that during the reaction of silane with water, in this stoichiometry 0.5 mol of water per mol alkoxy group, the reaction may be terminated before having reached an equilibrium, i.e., before the silsesquioxane has formed. The above-described coating agents may be produced on-site or obtained from a supplier, such as Sigma Aldrich, or any of the other suppliers.

[0034] In one or more embodiments, an acidic or basic catalyst may be required to complete the conversion of the precursor, i.e., the reaction of the precursor with water.

[0035] In some embodiments, the composition may be created with a precursor containing Si. Such precursors may comprise, (3-aminopropyl) triethoxysilane ("GAPS"), (3-glycidoxypropyl) trimethoxysilane ("GLYMO"), diethoxy (3-glycidoxypropyl) methylsilane, silsesquioxanes, poly(3-aminopropyl) silsesquioxane, poly (3-glycidoxypropyl) silsesquioxane, or a combination thereof. Again, these precursors may be produced on-site or obtained from a supplier, such as Sigma Aldrich.

[0036] In a general aspect, a composition for a glass substrate coating includes the precursor and an additive, where a ratio of water in the additive to the precursor is less than about 0.5 moles of water per mole alkoxy group in the precursor. In this regard, some more detailed discussion and examples are provided below.

[0037] In one or more embodiments, the composition may comprise silsesquioxanes, which are obtained by adding 0.5 mol of water to 1 mol per alkoxy group, or to 1 mol of the precursor R' -Si (OR)₃, as follows: n R'-Si(OR)₃ + 1.5 n H₂O → - (R' -SiO_x.₅)n- + 3 n ROH. [0038] While stirring n moles of the amino silane precursor in a PE bottle with a cap, 1.5 n moles of distilled water are slowly added. Then, the bottle is closed to avoid further penetration of humidity into the solution. The exothermic generation of ethanol during the formation of silsesquioxanes (i.e., the reaction of amino silane with water) leads to an increase of the pressure of the bottle. Thus, during some period of time, such as the first 30 minutes, the bottle may be opened from time to time to release this pressure. The reaction is then allowed to take place for a sufficient time, such as at least two days. Finally, this stock solution can be diluted with pure ethanol according to coating requirements .

[0039] In one or more embodiments, the composition may comprise SiO₂, by taking 1 mol of the precursor containing Si

(in this case tetraethyl orthosilicate ("TEOS")) and mixing it with less than 2 mol of water. While stirring n moles of the silane precursor in a PE bottle with a cap, less than 2 n moles of distilled water are slowly added. In some embodiments, additional additives may be used with water, such as at least a catalyst, for example, hydrogen chloride ("HCl"). The reaction is then allowed to take place for a sufficient time, such as at least two hours.

[0040] In some embodiments, a composition may be created with a precursor containing Ti . Such precursors may comprise Ti alkoxides such as tetraisopropyl orthotitanate ("Ti(OPr)₄"), titanium methacrylate triisopropoxide ("TiOPr-MA"), or a combination thereof. These precursors may be produced on-site or obtained from a supplier, such as Sigma Aldrich or ABCR Germany, or any of the other known suppliers.

[0041] In an embodiment, a composition may comprise precursor (s) of TiO₂, by taking 1 mol of the precursor containing Ti (in this case Ti(OPr)₄) and chelating same with 1 mol of the additive ethyl acetoacetate ("AcAc") to prevent very fast hydrolysis. The small amount of water additive used for hydrolysis may be obtained from the humidity of the ambient air. Isopropanol may be used as a solvent to dilute the composition as necessary. For the methacrylate (MA) containing TiO₂ coatings, the respective precursor may be diluted in isopropanol and applied by dip coating on the substrates. Thermal curing may be carried out at 200 deg C. Additionally or alternatively, UV curing may be performed.

[0042] It is noted that surfactants may be useful in increasing the wetting between the coating 112 (when in solution) and the surface of the substrate 100.

[0043] Reference is now made to FIG. 6, which is a table listing changes in Weibull modulus and failure strength for a number of coating compositions and processes used on Coming's EAGLE™ glass substrates according to various aspects of the present invention. In the examples illustrated in FIG. 6, the glass substrate specimens were indented to create reproducible strength limiting flaws on the surface that enable examination of the effectiveness of the coating, and that simulate production conditions where large size defects might be present . The references to Vickers 1 and Vickers 2 relate to two different batches of glass samples. The term "bare" in FIG. 7 refers to glass samples that were not indented and that come from the same batch as used for Vickers 1 samples .

[0044] The indentation procedure was carried out to obtain flaws in an otherwise pristine surface (obtained from fusion draw) . Without indentation, almost no defects on the surface of the glass would be present. The indentation procedure resulted in good references and reliable substrates for coating and measurements . The repeatability in the defect creation led to reliable scientific comparisons of different coatings and processes. It is noted, however, that the aforementioned Vickers indents were just models for the types of defects that might occur in practice. In practice, defects might be present on all six surfaces of the glass, i.e., on top, bottom and/or edges. Thus, for the purposes of discussion herein the edges of the glass are included in the term "surface".

[0045] After indentation and before coating, the specimens were aged for about 24 hours including a pyrolysis treatment at 500 degrees Celsius for about 5 hours. This treatment is intended for post indentation stress relaxation, and for rendering the surface more hydrophilic by bringing the OH groups to the glass/air interface thus improving adhesion. This process was carried out to assure the quality of the indented glass samples (taken as a reference) , but does not contribute to strengthening itself. Film deposition took place by dip coating with a withdrawal rate of 5 or 10 cm/minute, which was followed by drying (in air) and heat treatment.

[0046] Coating thickness and curing temperatures should be carefully selected to increase, if not maximize, both the Weibull modulus and failure strength of the glass substrate. The most improved coating found during experimentation in accordance with various aspects of the present invention is the combination of poly (3-aminopropyl) silsesquioxane and poly(3- glycidoxypropyl) silsesquioxane, with a curing temperature at 200 degrees Celsius and a coating thickness of 66 nm. In that experiment, the Weibull modulus increased by 603% and the failure strength increased by 539%. For the coatings with a thickness of less than about 3000 nm, the Weibull modulus increased significantly compared to that of the uncoated reference samples . The increase in failure strength was up to nine-fold relative to the failure strength of the uncoated specimen. The sample having a coating of 3700 nm thick was made to test an extreme, and resulted in a reduced Weibull modulus .

[0047] The results illustrated in FIG. 6 may be compared with the prior art coatings and processes (also used on Coming's EAGLE™ glass substrates) shown in FIG. 7. EAS (aminosilane and epoxysilane hydrolysed with stoichiometrical excess of water) and SiO₂ have been used in the prior art. Vickers 1 and "bare" refer to different substrates, each with the same glass type and thickness, but Vickers 1 includes an artificial defect, while "bare" does not include an artificial defect (only handling defects).

[0048] Although the invention herein has been described with reference to particular embodiments, it is to be understood that these embodiments are merely illustrative of the principles and applications of the present invention. It is therefore to be understood that numerous modifications may be made to the illustrative embodiments and that other arrangements may be devised without departing from the spirit and scope of the present invention as defined by the appended claims .

Claims

1. A composition for a glass substrate coating, comprising: a precursor; and an additive, wherein a ratio of water in said additive to said precursor is less than about 0.5 moles of water per mole and per alkoxy group in the precursor.

2. The composition of claim 1, wherein the ratio of water in said additive to said precursor is at least one of: (i) less than about 0.17 to about 0.5 moles of water per mol of precursor per alkoxy group; (ii) less than about 0.33 to about 0.5 moles of water per mol of precursor per alkoxy group; and (iii) less than about 0.33 moles of water per mol of precursor per alkoxy group.

3. The composition of claim 2, wherein the precursor contains from 1 to 4 alkoxy groups .

4. The composition of claim 1, wherein one of: the precursor contains 1 alkoxy group, and the amount of water is less than about 0.5 moles of water per mole of the precursor; the precursor contains 2 alkoxy groups, and the amount of water is less than about 1.0 moles of water per mole of the precursor; the precursor contains 3 alkoxy groups, and the amount of water is less than about 1.5 moles of water per mole of the precursor; and the precursor contains 4 alkoxy groups, and the amount of water is less than about 2.0 moles of water per mole of the precursor.

5. A composition in accordance with claim 1, wherein said precursor contains Si, Ti, cross linkable moieties comprising organic functionalities, cross linkable moieties comprising inorganic functionalities, or any combination thereof.

6. A composition in accordance with claim 1, wherein said composition contains a diluting solvent.

7. A composition in accordance with claim 6, wherein said diluting solvent includes at least one of: an organic solvent containing one or more hydroxyl groups, ethanol, isopropanol, glycol, ethylene glycol, and water.

8. A composition in accordance with claim 1, wherein said additive comprises at least one of: water, aminosilane, (3- aminopropyl) triethoxysilane, epoxysilane, (3-glycidoxypropyl) trimethoxysilane, poly(3-aminopropyl) silsesquioxane, poly (3- glycidoxypropyl) silsesquioxane, and one or more other silsesquioxanes .

9. A composition in accordance with claim 8, wherein said additive further comprises at least one of: a catalyst, organic acids or bases, inorganic acids or bases, and hydrogen chloride.

10. A composition in accordance with claim 8, wherein said additive further comprises at least one of: a chelating agent, and ethyl acetoacetate.

11. A composition in accordance with claim 1, wherein said additive for said precursor is water only derived from humidity of ambient air.

12. A composition in accordance with claim 5, wherein said precursor containing Si is (3-aminopropyl) triethoxysilane, (3-glycidoxypropyl) trimethoxysilane, diethoxy (3-glycidoxypropyl) methylsilane, poly (3-aminopropyl) silsesquioxane, poly (3-glycidoxypropyl) silsesquioxane, any other silsesquioxanes, and/or a combination thereof.

13. A composition in accordance with claim 5, wherein said precursor containing Ti is Ti alkoxide, tetraisopropyl orthotitanate, titanium methacrylate triisopropoxide, and/or a combination thereof .

14. A composition in accordance with claim 1, wherein said composition contains cross linkable silsesquioxanes, a partially hydrolysed Ti alkoxide, a partially hydrolysed amino- and/or epoxy silane, any reaction products thereof, poly (3- aminopropyl) silsesquioxane, poly (3-glycidoxypropyl) silsesquioxane, and/or poly (3-aminopropyl) silsesquioxane/poly (3-glycidoxypropyl) silsesquioxane .

15. A method of creating a composition for a glass substrate coating for strengthening, comprising: mixing a precursor and at least one additive, wherein a ratio of water in said additive to said precursor is less than about 0.5 moles of water per mole and per alkoxy group in the precursor; and allowing the mixture to have time for the reaction between the precursor and the additives to take place.

16. The method of claim 15, wherein the ratio of water in said additive to said precursor is at least one of: (i) less than about 0.17 to about 0.5 moles of water per mol of precursor per alkoxy group; (ii) less than about 0.33 to about 0.5 moles of water per mol of precursor per alkoxy group; and (iii) less than about 0.33 moles of water per mol of precursor per alkoxy group.

17. The method of claim 16, wherein the precursor contains from 1 to 4 alkoxy groups .

18. The method of claim 15, wherein one of: the precursor contains 1 alkoxy group, and the amount of water is less than about 0.5 moles of water per mole of the precursor; the precursor contains 2 alkoxy groups, and the amount of water is less than about 1.0 moles of water per mole of the precursor; the precursor contains 3 alkoxy groups, and the amount of water is less than about 1.5 moles of water per mole of the precursor; and the precursor contains 4 alkoxy groups , and the amount of water is less than about 2.0 moles of water per mole of the precursor.

19. A method in accordance with claim 15, further comprising diluting the reaction mixture.

20. A method in accordance with claim 15, wherein said precursor contains at least one of: Si, Ti, cross linkable moieties comprising organic functionalities, cross linkable moieties comprising inorganic functionalities, and/or any combination thereof .

21. A method in accordance with claim 15, further comprising: diluting said composition using an organic solvent, comprising at least one of an organic solvent containing one or more hydroxyl groups, ethanol, isopropanol, glycol, ethylene glycol, and water.

22. A method in accordance with claim 15, wherein said additive comprises at least one of: water, aminosilane, (3-aminopropyl) triethoxysilane, epoxysilane, (3-glycidoxypropyl) trimethoxysilane, poly(3- aminopropyl) silsesquioxane, poly (3-glycidoxypropyl) silsesquioxane, and/or one or more silsesquioxanes; a catalyst, organic acids or bases, inorganic acids or bases, and/or hydrogen chloride; a chelating agent, and/or ethyl acetoacetate,- any combination of the above; and any reaction products of the above.

23. A method in accordance with claim 15, further comprising terminating a reaction of silane with said water before having reached an equilibrium, which is before silsesquioxane has formed.

24. A method in accordance with claim 15, wherein said additive comprising water is only derived from humidity of ambient air is used.

25. A method in accordance with claim 24, wherein said Si precursor comprises at least one of: amino silane (3- aminopropyl) triethoxysilane, epoxy silane (3-glycidoxypropyl) trimethoxysilane, diethoxy (3-glycidoxypropyl) methylsilane, poly (3-aminopropyl) silsesquioxane, and/or poly(3- glycidoxypropyl) silsesquioxane, and/or any other silsesquioxanes .

26. A method in accordance with claim 24, wherein said Ti precursor comprises at least one of: one or more Ti alkoxides, tetraisopropyl orthotitanate, and titanium methacrylate triisopropoxide .

27. A method of creating one coating layer or a multilayer coating for a glass substrate, comprising: mixing a precursor and an additive, wherein a ratio of water in said additive to said precursor is less than about 0.5 moles of water per mole and per alkoxy group in the precursor; allowing the mixture to have time for the reaction between the precursor and the additives to take place; diluting the composition; adjusting a viscosity of the composition; applying the diluted, viscosity adjusted composition to a glass substrate to form a single coating layer or a multi-layer coating; and curing both said glass substrate and said coating layer at moderately elevated temperature.

28. A method in accordance with claim 27, wherein said precursor contains at least one of: Si, Ti, cross linkable moieties comprising organic functionalities, cross linkable moieties comprising inorganic functionalities, and/or any combination thereof .

29. A method in accordance with claim 27, further comprising diluting said composition with a solvent, comprising at least one of: an organic solvent containing one or more hydroxyl groups, ethanol, isopropanol, glycol, ethylene glycol, and water.

30. A method in accordance with claim 27, wherein said additive comprises at least one of: water, aminosilane, (3-aminopropyl) triethoxysilane, epoxysilane, (3-glycidoxypropyl) trimethoxysilane, poly (3- aminopropyl) silsesquioxane, poly (3-glycidoxypropyl) silsesquioxane, and/or one or more silsesquioxanes; a catalyst, organic acids or bases, inorganic acids or bases, and/or hydrogen chloride; a chelating agent, and/or ethyl acetoacetate; any combination of the above; and any reaction products of the above.

31. A method in accordance with claim 27, wherein said additive comprising water is only derived from humidity of ambient air is used.

32. A method in accordance with claim 31, wherein said Si precursor comprises at least one of: amino silane (3- aminopropyl) triethoxysilane, epoxy silane (3-glycidoxypropyl) trimethoxysilane, diethoxy (3-glycidoxypropyl) methylsilane, poly (3-aminopropyl) silsesquioxane, poly(3-glycidoxypropyl) silsesquioxane, and/or one or more silsesquioxanes, and/or a combination thereof .

33. A method in accordance with claim 31, wherein said Ti precursor comprises at least one of: Ti alkoxide, titanium methacrylate triisopropoxide, or a combination thereof.

34. A method in accordance with claim 27, wherein at least one of a dip coating process and any other coating process is used to apply one or more coating layers such that a thickness of about 5 nm to about 500 nm in the coating is achieved after curing.

35. A method in accordance with claim 27, further comprising at least one of: thermally curing, UV curing, and edge curing the coated substrate.

36. A method in accordance with claim 27, wherein said temperature is at least one of: about 80 degrees Celsius to about 500 degrees Celsius, and about 80 degrees Celsius to about 200 degrees Celsius.