Method for cleaning a glass surface

Abstract

A cleaning composition for cleaning a glass surface includes from about 0.4 mol / L to about 1.7 mol / L of HNO3, from about 0.5 mol / L to about 1.8 mol / L of acetic acid, and from about 6.0 mol / L to about 14.0 mol / L of phosphoric acid. The phosphoric acid is an acid having at least one phosphoric acid functional group. Also disclosed is a method of making a glass article, wherein the method comprises cleaning at least one surface of the glass article with the cleaning composition. At least one surface of the glass article has organic contaminants, inorganic particles, or both deposited on the surface, and cleaning the at least one surface of the glass article includes contacting the at least one surface with a cleaning composition.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of priority under patent law to U.S. Provisional Application Serial No. 63 / 592,365, filed on October 23, 2023, the contents of which are relied upon and incorporated herein by reference in their entirety. Technical Field

[0003] The present description relates generally to methods for cleaning glass surfaces, and more particularly, to methods for cleaning glass surfaces having organic compounds, inorganic particles, or both deposited on the glass surfaces. Background Art

[0004] Glass cleaning is an important process in the glass manufacturing industry for producing clean surfaces with low particle counts. For example, for strengthened glass, such as but not limited to automotive glass or glass for personal electronic devices, the presence of particles deposited on the glass surface may block certain surface areas during the ion exchange strengthening process, which can lead to surface defects and reduced product yield. For display glass and advanced optical components, the glass has even more stringent standards for surface particle counts because the presence of particles on the surface can not only cause coating peeling during manufacturing, but also cause thin film transistor (TFT) failures and device failures in downstream processes. Particles on the glass surface may be caused by the surface polishing process, which may utilize inorganic particles to polish the glass surface. In addition to polishing particles deposited on the glass surface, another source of contamination on the glass surface may include organic pollutants from processing, environmental pollution, handling, packaging, etc. Summary of the invention

[0005]

[0006] Therefore, there is a continuing need for improved cleaning compositions and methods for cleaning glass surfaces to remove inorganic particles, organic compounds, or both from the glass surfaces.

[0006] In a first aspect disclosed herein, a method for manufacturing a glass article is disclosed. The method may include cleaning at least one surface of the glass article, wherein at least one surface of the glass article includes organic contaminants, inorganic particles, or both deposited on the at least one surface. Cleaning at least one surface of the glass article may include contacting at least one surface of the glass article with a cleaning composition comprising about 0.4 mol / L to about 1.7 mol / L HNO3; about 0.5 mol / L to about 1.8 mol / L acetic acid; and about 6.0 mol / L to about 14.0 mol / L phosphoric acid. Phosphoric acid is an acid having at least one phosphoric acid functional group.

[0007] A second aspect disclosed herein may include the first aspect, wherein cleaning at least one surface may include ultrasonically cleaning at least one surface of the glass article with a cleaning composition, rinsing the at least one surface with water, ultrasonically cleaning the at least one surface with water, and drying the at least one surface under an inert atmosphere.

[0008] A third aspect disclosed herein may include the second aspect, comprising ultrasonically cleaning at least one surface with a cleaning composition at a frequency of about 20 Mhz to about 80 Mhz.

[0009] A fourth aspect disclosed herein may include any of the second or third aspects, comprising ultrasonically cleaning at least one surface with the cleaning composition for about 1 minute to about 60 minutes.

[0010] A fifth aspect disclosed herein may include any of the second to fourth aspects, comprising ultrasonically cleaning at least one surface with a cleaning composition at a temperature of about 35°C to about 95°C.

[0011] A sixth aspect disclosed herein may include any one of the second to fifth aspects, comprising rinsing the at least one surface with water for about 1 minute to about 30 minutes.

[0012] A seventh aspect disclosed herein may include any of the second to sixth aspects, including rinsing the at least one surface with water at a temperature of about 35°C to about 95°C.

[0013] An eighth aspect disclosed herein may include any one of the second to seventh aspects, comprising ultrasonically cleaning at least one surface with water for about 1 minute to about 30 minutes.

[0014] A ninth aspect disclosed herein may include any one of the second to eighth aspects, comprising ultrasonically cleaning at least one surface with water at a temperature of 35°C to 95°C.

[0015] A tenth aspect disclosed herein may include any one of the first to ninth aspects, wherein the inert atmosphere may include nitrogen.

[0016] An eleventh aspect disclosed herein may include any one of the first to tenth aspects, wherein the removal depth of at least one surface of the glass article after cleaning may be about 1 nm to about 20 nm.

[0017] A twelfth aspect disclosed herein may include any one of the first to eleventh aspects, wherein the removal depth of at least one surface of the glass article after cleaning may be less than or equal to 20 nm, less than or equal to 10 nm, less than or equal to 7 nm, or even less than or equal to 4 nm.

[0018] A thirteenth aspect disclosed herein may include any one of the first to twelfth aspects, wherein the surface roughness of at least one surface of the glass article may increase by less than or equal to 10% after cleaning.

[0019] A fourteenth aspect disclosed herein may include any one of the first to thirteenth aspects, wherein the surface roughness of at least one glass surface may increase by less than or equal to 5% after cleaning.

[0020] A fifteenth aspect disclosed herein may include any one of the first to fourteenth aspects, and further includes forming a glass article, wherein forming the glass article may include polishing at least one surface of the glass article with CeO2 particles, and the polishing results in residual CeO2 particles adhering to at least one surface of the glass article.

[0021] A sixteenth aspect disclosed herein may include the fifteenth aspect, wherein when at least one surface of the glass article is contacted with the cleaning composition, the residual CeO 2 particles may be dry on the at least one surface.

[0022] A seventeenth aspect disclosed herein may include any of the fifteenth or sixteenth aspects, wherein after cleaning the at least one surface, the amount of CeO2 particles on at least one surface of the glass article may be less than or equal to 600 particles / cm 2 .

[0023] The eighteenth aspect disclosed herein may include any one of the first to seventeenth aspects, wherein the phosphoric acid may be selected from H3PO4, H4P2O7, H5P3O 10 and organophosphates.

[0024] A nineteenth aspect disclosed herein may include any one of the first to eighteenth aspects, wherein the phosphoric acid may be H3PO4.

[0025] A twentieth aspect disclosed herein may include any one of the first to nineteenth aspects, wherein the cleaning composition may have a pH of about -3 to about -1.

[0026] A twenty-first aspect disclosed herein may include any one of the first to twentieth aspects, wherein the cleaning composition does not include a fluorine-containing compound.

[0027] A twenty-second aspect disclosed herein may include any one of the first to twenty-first aspects, wherein the cleaning composition may include about 0.6 mol / L to about 0.9 mol / L of HNO 3 .

[0028] A twenty-third aspect disclosed herein may include any one of the first to twenty-second aspects, wherein the cleaning composition may include about 0.7 mol / L to 1.0 mol / L of acetic acid.

[0029] A twenty-fourth aspect disclosed herein may include any one of the first to twenty-third aspects, wherein the cleaning composition may include about 7.0 mol / L to about 14.0 mol / L or about 9.0 mol / L to about 13.0 mol / L of phosphoric acid.

[0030] The twenty-fifth aspect disclosed herein may include any one of the first to twenty-fourth aspects, wherein the cleaning composition may consist of or consist essentially of an aqueous solution, wherein the aqueous solution consists of or consists essentially of: about 0.4 mol / L to about 1.7 mol / L HNO3; about 0.5 mol / L to about 1.8 mol / L acetic acid; about 6.0 mol / L to about 14.0 mol / L H3PO4; and the remainder water.

[0031] The twenty-sixth aspect disclosed herein may include any one of the first to twenty-fifth aspects, wherein the cleaning composition may consist of or consist essentially of an aqueous solution, wherein the aqueous solution consists of or consists essentially of: about 0.6 mol / L to about 0.9 mol / L HNO3; about 0.7 mol / L to about 1.0 mol / L acetic acid; about 9.0 mol / L to about 14.0 mol / L H3PO4; and the balance water.

[0032] Additional features and advantages of the embodiments described herein will be set forth in the detailed description that follows, and in part will be apparent to those skilled in the art or will be learned by practicing the embodiments described herein, including the detailed description that follows, the claims, and the accompanying drawings.

[0033] It should be understood that both the foregoing general description and the following detailed description describe various embodiments and are intended to provide an overview or framework for understanding the nature and character of the claimed subject matter. The accompanying drawings are included to provide a further understanding of the various embodiments and are incorporated into and constitute a part of this specification. The drawings illustrate various embodiments described herein and, together with the description, serve to explain the principles and operation of the claimed subject matter. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 depicts a flow chart of a process for cleaning a glass surface according to embodiments shown and described herein;

[0035] Figure 2 depicts a flow chart for producing a polished glass article according to the embodiments shown and described herein;

[0036] Figure 3 schematically depicts a mechanism for glass polishing using cerium oxide nanoparticles according to embodiments shown and described herein;

[0037] Figure 4 schematically depicts the bonding of cerium oxide nanoparticles to a glass surface after polishing according to embodiments shown and described herein;

[0038] Figure 5 depicts a flow chart of a method for producing and packaging a plurality of glass articles from a glass sheet according to embodiments shown and described herein;

[0039] Figure 6 graphically depicts particle density (y-axis) on a glass surface after polishing with cerium oxide particles and then cleaning with a cleaning composition disclosed herein, according to embodiments shown and described herein, compared to conventional cleaners;

[0040] Figure 7 is a scanning electron microscope (SEM) image of a glass surface polished with cerium nanoparticles at pH 7 and then cleaned with a conventional alkaline pH cleaner;

[0041] Figure 8 is a SEM image of a glass surface polished with cerium nanoparticles at pH 7 and then cleaned with a conventional neutral pH cleaner;

[0042] Fig. 9 is a SEM image of a glass surface polished with cerium nanoparticles at pH 7 and then cleaned with a cleaning composition according to embodiments shown and described herein;

[0043] Fig.10 is a SEM image of a glass surface polished with cerium nanoparticles at pH 9 and then cleaned with a conventional alkaline pH cleaner;

[0044] Fig.11 is a SEM image of a glass surface polished with cerium nanoparticles at pH 9 and then cleaned with a conventional neutral pH cleaner;

[0045] Fig.12 is a SEM image of a glass surface polished with cerium nanoparticles at pH 9 and then cleaned with a cleaning composition according to embodiments shown and described herein;

[0046] Fig.13 graphically depicts particle density (y-axis) on a glass surface after polishing with cerium oxide particles from different suppliers and at different polishing pHs, and then cleaning with a cleaning composition disclosed herein, according to embodiments shown and described herein;

[0047] Fig.14graphically depicts particle density (y-axis) on a glass surface after polishing with cerium oxide particles and then cleaning with a cleaning composition disclosed herein, according to embodiments shown and described herein, compared to a conventional cleaner of a single type of cerium oxide particles at a fixed pH;

[0048] Fig.15 graphically depicts the zeta potential (y-axis) of CeO2 particles in solution after polishing with cerium oxide particles from various suppliers and then cleaning with the cleaning composition disclosed herein at pH 7 and pH 9, compared to conventional cleaners, according to embodiments shown and described herein;

[0049] Fig.16 graphically depicts the zeta potential (y-axis) of CeO particles in solution after polishing with CeO particles from different suppliers at pH 7 and pH 9 and then cleaning with cleaning compositions of different pH as a function of the pH of the cleaning solution (x-axis) according to embodiments shown and described herein;

[0050] Fig.17 is a line scan dark field scattering image of a surface of a glass article before spraying the surface with a slurry comprising cerium oxide nanoparticles according to embodiments shown and described herein;

[0051] Fig.18 According to the embodiments shown and described herein, after spraying the surface with a slurry containing cerium oxide nanoparticles and allowing the surface to dry Fig.18 A line scan dark field scattering image of the surface of the glass article; and

[0052] Fig.19 According to the embodiments shown and described herein, after cleaning the surface with the cleaning composition Fig.19 Line scan dark field scattering image of the glass surface. DETAILED DESCRIPTION

[0053] Specific embodiments of the application are now described. However, the present disclosure can be implemented in different forms and should not be construed as being limited to the embodiments set forth in the present disclosure. On the contrary, these embodiments are provided so that the present disclosure will be thorough and complete, and the scope of this theme will be fully conveyed to those skilled in the art. Wherever possible, the same reference numerals will be used in all figures to refer to the same or similar parts.

[0054] Embodiments of the present disclosure relate to cleaning compositions for cleaning glass surfaces. The cleaning composition may include nitric acid (HNO ), acetic acid and phosphoric acid, wherein the phosphoric acid is an acid having at least one phosphoric acid functional group. Specifically, the cleaning composition may include about 0.4 mol / L to about 1.7 mol / L of HNO , about 0.5 mol / L to about 1.8 mol / L of acetic acid and about 6.0 mol / L to about 14.0 mol / L of phosphoric acid. The cleaning composition and the method for cleaning glass surfaces with the cleaning composition can be used to remove organic and inorganic contaminants from the glass surface, such as metal oxide particles used in glass polishing and organic compounds from manufacturing, processing, packaging, environmental sources or other sources of organic compounds.

[0055] The present disclosure also relates to a method for cleaning a glass surface using the cleaning composition. Figure 1 , the method 100 disclosed herein may include cleaning at least one surface of the glass article in a cleaning step 110, wherein the at least one surface of the glass article includes organic contaminants, inorganic particles, or both deposited on the at least one surface, and cleaning the at least one surface of the glass article includes contacting the at least one surface with a cleaning composition comprising about 0.4 mol / L to about 1.7 mol / L HNO3, about 0.5 mol / L to about 1.8 mol / L acetic acid, and about 6.0 mol / L to about 14.0 mol / L phosphoric acid, wherein the phosphoric acid is an acid having at least one phosphoric acid functional group. The method disclosed herein may also include rinsing the glass surface with water, ultrasonically cleaning the at least one surface with water, and drying the at least one surface under an inert atmosphere.

[0056] Directional terms (eg, up, down, right, left, front, back, top, bottom) as used herein refer only to the drawn figures and the coordinate axes provided therewith and are not intended to indicate absolute directions.

[0057] Unless otherwise expressly stated, it is not intended that any method set forth herein be interpreted as requiring that its steps be performed in a particular order, nor is it intended to require a particular orientation of any apparatus. Thus, in the absence of a method claim actually reciting the order in which its steps are to be followed, or of any apparatus claim actually reciting the order or orientation of individual components, or in the absence of additional specific statements in the claims or description that the steps are to be limited to a particular order, or reciting a particular order or orientation of apparatus components, it is not intended that order or orientation be inferred in any respect. This applies to any possible non-expressive basis for interpretation, including: logical issues regarding the arrangement of steps, operational flow, order of components, or orientation of components; obvious meaning derived from grammatical organization or punctuation; and the number or type of embodiments described in this specification.

[0058] As used herein, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a" component includes aspects having two or more such components unless the context clearly dictates otherwise.

[0059] "About" As used herein, the term "about" means that quantities, sizes, formulations, parameters, and other quantities and features are not and need not be exact, but may be approximate and / or larger or smaller as necessary, reflecting tolerances, conversion factors, rounding, measurement errors, etc. and other factors known to those skilled in the art. In general, quantities, sizes, formulations, parameters, or other quantities or features are "about" or "approximately" whether or not such explicit indication is made.

[0060] It is noted that one or more of the claims may use the term "wherein" as a transitional phrase. For purposes of defining the present disclosure, it is noted that this term is introduced in the claims as an open transitional phrase to introduce a recitation of a list of structural features and should be interpreted in a manner similar to the more commonly used open introductory term "comprising."

[0061] As used herein, the terms "upstream" and "downstream" refer to the relative order of steps in the disclosed methods. For example, if method step A is performed before method step B, then method step A is upstream of method step B. Conversely, if method step B is performed before performing method step A, then method step A is downstream of method step B.

[0062] As used herein, the term "phosphoric acid" refers to any organic or inorganic acid containing at least one phosphoric acid functional group.

[0063] As previously discussed, glass cleaning is an important process in the glass manufacturing industry for producing clean surfaces with low particle counts. Particles on the glass surface may be caused by the surface polishing process, which may utilize inorganic particles to polish the glass surface. In addition to polishing particles deposited on the glass surface, another source of contamination of the glass surface may include organic contaminants from processing, environmental contamination, handling, packaging, etc. Cleaning the glass surface is a process that may occur many times during the manufacturing and / or finishing of glass products.

[0064] Reference now Figure 2 , schematically depicts an exemplary finishing process for finishing the surface of a glass product including a glass hard disk. Figure 2 As shown, one embodiment of the finishing process 200 may include multiple finishing and cleaning steps. For example, Figure 2The depicted finishing process 200 may include grinding 202, a first cleaning step 204 after grinding 202, a first measurement / inspection 206, a rough grinding step 208, a second cleaning step 210 after the rough grinding step 208, a second measurement / inspection 212, a first polishing step 214, a third cleaning step 216 after the first polishing step 214, a second polishing step 218, a fourth cleaning step 220 after the second polishing step 218, a third polishing step 222, a fifth cleaning step 224 after the third polishing step 222, a drying step 226, and a final measurement / inspection 228. Thus, a typical finishing process 200 may include multiple polishing steps and multiple cleaning steps.

[0065] During the polishing step, the glass surface is polished with a composition comprising inorganic oxide nanoparticles. Cerium oxide (ceria or CeO2) particles such as CeO2 nanoparticles are the most commonly used polishing materials for polishing glass products. Compared with silicon dioxide (SiO2) particles, CeO2 particles are cost-effective and can polish glass surfaces to meet the roughness requirements of most applications. However, the adhesion of CeO2 particles on the glass surface can be very strong, especially when CeO2 particles are dried on the glass surface, which can create additional challenges for CeO2 particles removed from the glass surface. The most commonly used cleaning method for removing CeO2 particles includes brush cleaning that mechanically removes part of the CeO2 particles, contacting the glass surface with an alkaline detergent that chemically removes the CeO2 particles, or a combination of the two. However, even if the polished glass surface is strictly mechanically and chemically cleaned using the above method, a large number of glass products (depending on their applications) that do not meet the particle count requirements in manufacturing will still be produced, resulting in reduced production and increased waste.

[0066] A widely accepted mechanism for glass polishing using CeO2 nanoparticles is a combination of physical and chemical processes. Figure 3 During glass polishing with CeO2 nanoparticles 302, in the presence of water, Ce-OH groups on the outer surface of CeO2 particles 302 react with SiOH on the glass surface to dissolve the top glass layer from the glass surface. Figure 4 Applying physical force (such as with pad 402) can also help remove glass particles from the glass surface by friction. During the polishing process, depending on the pH of the CeO2 nanoparticle slurry, the oxidation state of Ce may change from Ce to 4+ Change to Ce 3+ , which may affect the reaction rate of CeO2 with glass particles on the glass surface. In addition, the pH of the CeO2 particle slurry will also affect the zeta potential and particle size of the CeO2 particles, which in turn will also affect the polishing efficiency and cleaning efficiency.

[0067] The glass surface of the glass article may also accumulate organic contaminants during the finishing process, such as from processing, environmental contamination, handling, packaging, etc. As for the source of the organic contaminants, the type of organic contaminants may be different depending on the materials in contact with the glass article. However, in general, organic contaminants may include polar and non-polar organic compounds.

[0068] The present disclosure relates to cleaning compositions and methods for cleaning glass surfaces to remove inorganic particles (such as CeO2 particles from polishing processes) and organic contaminants (such as polar and non-polar organic compounds from processing, handling, packaging or other operations). The cleaning compositions disclosed herein are acidic cleaning compositions, which are aqueous solutions of nitric acid (HNO3), acetic acid and phosphoric acid. Phosphoric acid can be any organic or inorganic acid containing at least one phosphoric acid functional group in the molecule. In an embodiment, phosphoric acid can be phosphoric acid, phosphonic acid, organophosphonic acid, other phosphoric acid-containing acids or combinations thereof. The method for cleaning a glass surface may include contacting the glass surface with a cleaning composition disclosed herein, followed by one or more rinsing steps, and optionally performing one or more drying steps.

[0069] The cleaning compositions and cleaning processes disclosed herein show much better cleaning results in removing all types of contaminants from glass surfaces, including organic contaminants from processing and treatment and inorganic particles (i.e., CeO2 particles) from finishing, under wet and dry conditions after finishing. The cleaning compositions show the solvency of glass to help remove organic contaminants by dissolving the top layer of the glass surface. In addition, the cleaning compositions can be easily rinsed off the glass surface by water without leaving residues that cause secondary contamination.

[0070] The disclosed cleaning composition does not contain fluoric acid and represents a non-toxic chemistry that is not expected to require special environmental regulations for disposal, which can reduce waste disposal costs. Unlike conventional cleaners containing fluoric acid or harsh alkaline formulations, the disclosed cleaning composition and cleaning method only slightly attack the glass surface and have not been shown to cause pitting or surface roughness changes after cleaning. Among other features, the disclosed cleaning composition and cleaning method are compatible with current glass product manufacturing processes and can be easily scaled up and adopted in a manufacturing environment.

[0071] As previously discussed, the cleaning composition disclosed herein includes an aqueous solution comprising three active ingredients: (A) nitric acid (HNO3) (3-10 volume %); (B) acetic acid (3-10 volume %); and (C) phosphoric acid (40-90 volume %). The cleaning composition may be referred to herein as a PNA cleaning composition, wherein PNA is an acronym for phosphoric acid, nitric acid, and acetic acid. In an embodiment, the cleaning composition may be an aqueous composition comprising, consisting essentially of, or consisting of about 0.4 mol / L to about 1.7 mol / L HNO3, about 0.5 mol / L to about 1.8 mol / L acetic acid, about 6.0 mol / L to about 14.0 mol / L phosphoric acid, and water.

[0072] Without being bound by any particular theory, it is believed that the high cleaning ability of the PNA cleaning composition disclosed herein may be due to three factors: (1) the dissolving power of HNO3 and phosphoric acid, (2) the electrical interaction between the components of the PNA cleaning composition and the charged contaminant particles (such as CeO2 particles or polar organic compounds); and (3) after water rinsing, there is much less residue on the glass surface, which reduces secondary contamination after cleaning.

[0073] As previously discussed, the cleaning composition comprises nitric acid. In embodiments, the cleaning composition may comprise about 0.4 mol / L to about 1.7 mol / L nitric acid, such as about 0.4 mol / L to about 1.6 mol / L, about 0.4 mol / L to about 1.4 mol / L, about 0.4 mol / L to about 1.2 mol / L, about 0.4 mol / L to about 1.0 mol / L, about 0.4 mol / L to about 0.8 mol / L, about 0.4 mol / L to about 0.6 mol / L, about 0.6 mol / L to about 1.7 mol / L, about 0.6 mol / L to about 1.6 mol / L, about 0.6 mol / L to about 1.4 mol / L, about 0.6 mol / L to about 1.2 mol / L, about 0.6 mol / L to about 1.0 mol / L, about 0.6 mol / L to about 0.8 mol / L, about 0.8 mol / L to about 1.7 mol / L , about 0.8 mol / L to about 1.6 mol / L, about 0.8 mol / L to about 1.4 mol / L, about 0.8 mol / L to about 1.2 mol / L, about 0.8 mol / L to about 1.0 mol / L, about 1.0 mol / L to about 1.7 mol / L, about 1.0 mol / L to about 1.6 mol / L, about 1.0 mol / L to about 1.4 mol / L, about 1.0 mol / L to about 1.2 mol / L, about 1.2 mol / L to about 1.7 mol / L, about 1.2 mol / L to about 1.6 mol / L, about 1.2 mol / L to about 1.4 mol / L, about 1.4 mol / L to about 1.7 mol / L, about 1.4 mol / L to about 1.6 mol / L, about 1.6 mol / L to about 1.7 mol / L, or any combination of one or more of these ranges. In an embodiment, the cleaning composition may include from about 0.6 mol / L to about 0.9 mol / L HNO 3 .

[0074] In embodiments, nitric acid may be supplied as a 15.9 mole (M) stock solution, and the cleaning composition may include about 3 volume % to about 10 volume % HNO3 stock solution, based on the total volume of the cleaning composition. The volume percentage range may vary based on the molar concentration of the HNO3 stock solution used (e.g., a more concentrated HNO3 solution has a smaller volume percentage, while a more dilute HNO3 solution requires a larger volume percentage HNO3 solution). In embodiments, the cleaning composition may include about 3 volume % to about 8 volume %, about 3 volume % to about 6 volume %, about 4 volume % to about 10 volume %, about 4 volume % to about 8 volume %, about 4 volume % to about 6 volume % or about 4 volume % HNO3 stock solution, based on the total weight of the cleaning composition. In embodiments, the HNO3 stock solution may be about 5M to 20M HNO3, wherein concentrated HNO3 is about 20M HNO3. In embodiments, the HNO3 stock solution may be about 10 M to about 20 M, about 10 M to about 18 M, about 12 M to about 17 M, or about 14 M to about 16 M acetic acid.

[0075] As previously discussed, the cleaning composition comprises acetic acid. In embodiments, the cleaning composition may comprise about 0.5 mol / L to about 1.8 mol / L of acetic acid, such as about 0.5 mol / L to about 1.6 mol / L, about 0.5 mol / L to about 1.4 mol / L, about 0.5 mol / L to about 1.2 mol / L, about 0.5 mol / L to about 1.0 mol / L, about 0.5 mol / L to about 0.8 mol / L, about 0.5 mol / L to about 0.6 mol / L, about 0.6 mol / L to about 1.6 mol / L, about 0.6 mol / L to about 1.4 mol / L, about 0.5 mol / L to about 1.2 mol / L, about 0.5 mol / L to about 1.0 mol / L, about 0.5 mol / L to about 0.8 mol / L, about 0.5 mol / L to about 0.6 mol / L, about 0.6 mol / L to about 1.6 mol / L, about 0.6 mol / L to about 1.8 mol / L. From about 1.0mol / L to about 1.0mol / L, from about 0.6mol / L to about 0.8mol / L, from about 0.8mol / L to about 1.6mol / L, from about 0.8mol / L to about 1.4mol / L, from about 0.8mol / L to about 1.2mol / L, from about 0.8mol / L to about 1.0mol / L, from about 1.0mol / L to about 1.6mol / L, from about 1.0mol / L to about 1.4mol / L, from about 1.0mol / L to about 1.2mol / L, from about 1.2mol / L to about 1.6mol / L, from about 1.2mol / L to about 1.4mol / L, from about 1.4mol / L to about 1.6mol / L, or any combination of one or more of these ranges. In embodiments, the cleaning composition may include acetic acid in an amount of from about 0.7mol / L to about 1.0mol / L.

[0076] In embodiments, acetic acid may be supplied as a 17.45 molar (M) stock solution, and the cleaning composition may include about 3% to about 10% by volume of the acetic acid stock solution, based on the total volume of the cleaning composition. The volume percentage range may vary based on the molar concentration of the acetic acid stock solution used (e.g., a more concentrated acetic acid solution has a smaller volume percentage, while a more dilute acetic acid solution requires a larger volume percentage of acetic acid solution). In embodiments, the cleaning composition may include about 3% to about 8% by volume, about 3% to about 6% by volume, about 4% to about 10% by volume, about 4% to about 8% by volume, about 4% to about 6% by volume, or about 4% by volume of the acetic acid stock solution, based on the total weight of the cleaning composition. In embodiments, the acetic acid stock solution may be about 10M to 17.5M acetic acid, wherein glacial acetic acid (99.7%) is about 17.42M.

[0077] As previously discussed, the cleaning composition includes phosphoric acid. The phosphoric acid can be an acid having at least one phosphoric acid functional group. The phosphoric acid can include, but is not limited to, phosphonic acid (H3PO3), phosphoric acid (H3PO4), metaphosphoric acid ((HPO3) n ), hypophosphorous acid (H4P2O6), pyrophosphoric acid (H4P2O7), H5P3O 10 , organic phosphonic acid, other compounds containing phosphoric acid functional groups or combinations thereof. In an embodiment, the phosphoric acid can be selected from the group consisting of: phosphonic acid (H3PO3), phosphoric acid (H3PO4), metaphosphoric acid ((HPO3) n ), hypophosphorous acid (H4P2O6), pyrophosphoric acid (H4P2O7), H5P3O 10 , organic phosphonic acid, and combinations thereof. In embodiments, the cleaning composition may include phosphoric acid (H3PO4). In embodiments, the cleaning composition may include phosphonic acid (H3PO3). In embodiments, the cleaning composition may include a compound having the chemical formula R 1 -PO(OR 2 )(OR 3 ) of an organic phosphonic acid, wherein R 1 is a hydrocarbon group, and R 2 and R 3 It can be hydrogen or a hydrocarbon group. 2 and R 3 Can be the same or different.

[0078] In an embodiment, the cleaning composition may include about 6.0 mol / L to about 14.0 mol / L of phosphoric acid, such as about 6.0 mol / L to about 13.0 mol / L, about 6.0 mol / L to about 12 mol / L, about 6.0 mol / L to about 11.0 mol / L, about 6.0 mol / L to about 10.0 mol / L, about 6.0 mol / L to about 9.0 mol / L, about 6.0 mol / L to about 8.0 mol / L, about 7.0 mol / L to about 14 mol / L, about 7.0 mol / L to about 13.0mol / L, about 7.0mol / L to about 12.0mol / L, about 7.0mol / L to about 11.0mol / L, about 7.0mol / L to about 10.0mol / L, about 7.0mol / L to about 9.0mol / L, about 7.0mol / L to about 8.0mol / L, about 8.0mol / L to about 14.0mol / L, about 8.0mol / L to about 13.0mol / L, about 8.0mol / L to about 12.0mol / L, about 8.0mol / L to about 11.0mol / L, about 8.0mol / L to about 10.0mol / L, about 8.0mol / L to about 9.0mol / L, about 9.0mol / L to about 14.0mol / L, about 9.0mol / L to about 13.0mol / L, about 9.0mol / L to about 12.0mol / L, about 9.0mol / L to about 11.0mol / L, about 9.0mol / L to about 10.0mol / L, about 10.0mol / L to about 14.0mol / L, about 10.0mol / L to about 13.0mol / L, About 10.0 mol / L to about 12.0 mol / L, about 10.0 mol / L to about 11.0 mol / L, about 11.0 mol / L to about 14.0 mol / L, about 11.0 mol / L to about 13.0 mol / L, about 11.0 mol / L to about 12.0 mol / L, about 12.0 mol / L to about 14.0 mol / L, about 12.0 mol / L to about 13.0 mol / L, about 13.0 mol / L to about 14.0 mol / L, or any combination of one or more of these ranges.

[0079] In embodiments, phosphoric acid may be supplied as a stock solution of 14.8 moles (M) of H3PO4 in water, and the cleaning composition may include about 40% to about 94% by volume of the phosphoric acid stock solution, based on the total volume of the cleaning composition. The volume percentage range may vary based on the molar concentration of the phosphoric acid stock solution used (e.g., a more concentrated phosphoric acid solution has a smaller volume percentage, while a more dilute phosphoric acid solution requires a larger volume percentage of phosphoric acid solution). In embodiments, the cleaning composition may include about 40% to about 90% by volume, about 50% to about 90% by volume, about 50% to about 85% by volume, about 50% to about 80% by volume, about 70% to about 94% by volume, about 70% to about 90% by volume, or about 80% by volume of the phosphoric acid stock solution, based on the total weight of the cleaning composition. In embodiments, the phosphoric acid stock solution may be about 10M to 16M phosphoric acid.

[0080] The cleaning composition may also include water, which constitutes the remainder of the cleaning composition. In embodiments, water may be added as a part of a stock solution of HNO , acetic acid and phosphoric acid. In embodiments, supplementary water (except water from an acid stock solution) may be added to adjust the total ionic strength and component concentration of the cleaning composition. In embodiments, the cleaning composition may include supplementary water of about 0% by volume to about 44% added to the cleaning composition, which is except the water already included in the stock solution, such as about 0% by volume to about 40% by volume, about 0% by volume to about 30% by volume, about 0% by volume to about 20% by volume, about 0% by volume to about 10% by volume, about 5% by volume to about 44% by volume, about 5% by volume to about 40% by volume, about 5% by volume to about 30% by volume, about 5% by volume to about 20% by volume, about 5% by volume to about 10% by volume, or about 10% by volume. In an embodiment, the cleaning composition may include 80 vol% of a 14.8 M phosphoric acid stock solution, 5 vol% of a 15.9 M HNO3 stock solution, 5 vol% of a 17.45 M acetic acid stock solution, and the balance water (which may include about 10 vol% make-up water added to the cleaning composition).

[0081] In embodiments, cleaning compositions disclosed herein may include HNO3, acetic acid, phosphoric acid and water, consisting essentially of or consisting of, wherein HNO3 has a concentration of about 0.4 mol / L to about 1.7 mol / L, acetic acid has a concentration of about 0.5 mol / L to about 1.8 mol / L, and phosphoric acid has a concentration of about 6.0 mol / L to about 14.0 mol / L. In embodiments, cleaning compositions disclosed herein may include HNO3, acetic acid, phosphoric acid and water, consisting essentially of or consisting of, wherein HNO3 has a concentration of about 0.4 mol / L to about 1.7 mol / L, acetic acid has a concentration of about 0.5 mol / L to about 1.8 mol / L, and phosphoric acid has a concentration of about 7.0 mol / L to about 14.0 mol / L. Cleaning compositions may have a sub-range of any acidic component disclosed herein. In embodiments, cleaning compositions do not include fluorine-containing compounds. In embodiments, cleaning compositions may be substantially free of fluorine-containing compounds, such as having a fluorine-containing compound less than or equal to 500 ppm. In embodiments, the cleaning composition does not contain any intentionally added hydrofluoric acid (HF) or other fluorine-containing acids or fluorinated hydrocarbons.

[0082] The cleaning composition can be prepared by combining and mixing the individual acidic ingredients (ie, nitric acid, acetic acid, and phosphoric acid). Optionally, additional water can be added to the mixture of acidic ingredients to prepare the cleaning composition.

[0083] Cleaning compositions can be acidic.In embodiments, Cleaning compositions can have a pH of about -3 to about -1, such as about -3 to about -1.5, about -3 to about -2, about -3 to about -2.5, about -2.5 to about -1, about -2.5 to about -1.5, about -2.5 to about -2, about -2 to about -1, about -2 to about -1.5, about -1.5 to about -1, or one or more combinations in any of these scopes.Not bound by theory, it is believed that the zeta potential of the metal oxide particles (such as, for example, cerium oxide particles) used for polishing glass surfaces is reduced as the pH of the solution is reduced.The reduction in zeta potential may cause the stability of metal oxide particles in solution to decrease, which may cause metal oxide particles (for example, cerium oxide particles) to form aggregates and precipitate out from solution.This can remove metal oxide particles from the glass surface and can reduce or prevent metal oxide particles from being re-deposited on the glass surface.

[0084] Reference again Figure 1As previously discussed, the method 100 for cleaning a glass surface may include cleaning at least one surface of a glass article with a cleaning composition disclosed herein in a cleaning step 110. The surface of the glass article may include organic contaminants, inorganic particles, or both deposited on the surface. The cleaning composition may include any cleaning composition disclosed herein, such as, but not limited to, a cleaning composition comprising about 0.4 mol / L to about 1.7 mol / L of HNO3, about 0.5 mol / L to about 1.8 mol / L of acetic acid, about 7.0 mol / L to about 14.0 mol / L of phosphoric acid, and the remainder of water, wherein phosphoric acid is an acid having at least one phosphoric acid functional group. The method disclosed herein may also include rinsing the glass surface with water in step 120, ultrasonically cleaning at least one surface with water in step 130, and drying at least one surface under an inert atmosphere in step 140.

[0085] In the cleaning step 110 of method 100, at least one glass surface of a glass article can be cleaned with a cleaning composition disclosed herein. Cleaning at least one surface of a glass article may include contacting at least one surface with a cleaning composition disclosed herein. In an embodiment, cleaning at least one glass surface may include ultrasonic cleaning of at least one surface with a cleaning composition. In the process of ultrasonic cleaning of the surface of a glass article with a cleaning solution, a portion or all of the glass article may be immersed in a bath containing the cleaning composition. The glass surface of the glass article may be contacted with the cleaning composition at an elevated temperature (e.g., a temperature higher than room temperature (about 25° C.)) for a period of time sufficient to clean most or all organic and inorganic contaminants from the glass surface. The cleaning composition may have any composition or feature previously discussed herein for the cleaning composition.

[0086] In an embodiment, cleaning the glass surface of the glass article may include ultrasonically cleaning at least one surface with a cleaning composition in an ultrasonic parts cleaning machine, the cleaning machine being operable to ultrasonically agitate the cleaning composition during contact with the cleaning composition. Ultrasonic agitation can help remove contaminants from the glass surface and enter the bulk solution, which will be replaced by a fresher cleaning composition. Removing contaminants from the surface and replacing them with a fresher cleaning composition may help reduce or prevent contaminants from being re-deposited on the surface. Ultrasonic cleaning can be performed at an ultrasonic frequency setting of 20Mhz to 80Mhz, such as 20Mhz to 70Mhz, 20Mhz to 60Mhz, 20Mhz to 50Mhz, 20Mhz to 40Mhz, 20Mhz to 30Mhz, 30Mhz to 80Mhz, 30Mhz to 70Mhz, 30Mhz to 60Mhz, 30Mhz to 50Mhz, 30Mhz to 50Mhz, 30Mhz to 60Mhz, 30Mhz to 5 ...50Mhz, 30Mhz to 50Mhz, 30Mhz to 50Mhz, 30Mhz to 50Mhz, 30Mhz to 50Mhz, 30Mhz to 50Mhz, 30Mhz to 50Mhz, 30Mh to 40Mhz, 40Mhz to 80Mhz, 40Mhz to 70Mhz, 40Mhz to 60Mhz, 40Mhz to 50Mhz, 50Mhz to 80Mhz, 50Mhz to 70Mhz, 50Mhz to 60Mhz, 60Mhz to 80Mhz, 60Mhz to 70Mhz, 70Mhz to 80Mhz, or any combination of one or more of these ranges.

[0087] In an embodiment, cleaning the glass surface of a glass article with a cleaning composition may be performed at a temperature above room temperature, such as at a temperature of about 35°C to about 95°C, such as about 35°C to about 90°C, about 35°C to about 85°C, about 35°C to about 80°C, about 35°C to about 75°C, about 35°C to about 70°C, about 35°C to about 65°C, about 35°C to about 60°C, about 35°C to about 55°C, about 35°C to about 50°C, about 35°C to about 45°C, about 35°C to about 40°C, about 40°C to about 95°C, about 40°C to about 90°C, about 40°C to about 85°C, about 40°C to about 80°C, about 40°C to about about 75°C, about 40°C to about 70°C, about 40°C to about 65°C, about 40°C to about 60°C, about 40°C to about 55°C, about 40°C to about 50°C, about 40°C to about 45°C, about 45°C to about 95°C, about 45°C to about 90°C, about 45°C to about 85°C, about 45°C to about 80°C, about 45°C to about 75°C, about 45°C to about 70°C, about 45°C to about 65°C, about 45°C to about 60°C, about 45°C to about 55°C, about 45°C to about 50°C, about 50°C to about 95°C, about 50°C to about 90°C, about 50°C to about 85°C, about 50°C to about 80°C, about 50°C to about 75°C, about 50°C to about 70°C, about 50°C to about 65°C, about 50°C to about 60°C, about 50°C to about 55°C, about 55°C to about 95°C, about 55°C to about 90°C, about 55°C to about 85°C, about 55°C to about 80°C, about 55°C to about 75°C, about 55°C to about 70°C, about 55°C to about 65°C, about 55°C to about 60°C, about 60°C to about 95°C, about 60°C to about 90°C, about 60°C to about 85°C, about 60°C to about 80°C, about 60°C to about 75°C, about 60°C to about 70°C, about 60°C to about 65°C, about 65°C to about 95°C, about 65°C to about ℃ to about 0 ℃, about 65 ℃ to about 85 ℃, about 65 ℃ to about 80 ℃, about 65 ℃ to about 75 ℃, about 65 ℃ to about 70 ℃, about 70 ℃ to about 95 ℃, about 70 ℃ to about 90 ℃, about 70 ℃ to about 85 ℃, about 70 ℃ to about 80 ℃, about 70 ℃ to about 75 ℃, about 75 ℃ to about 95 ℃, about 75 ℃ to about 90 ℃, about 75 ℃ to about 85 ℃, about 75 ℃ to about 90 ℃, about 75 ℃ to about 85 ℃, about 75 ℃ to about 80 ℃, about 80 ℃ to about 95 ℃, about 80 ℃ to about 90 ℃, about 80 ℃ to about 85 ℃, about 85 ℃ to about 95 ℃, about 85 ℃ to about 90 ℃, or any combination of one or more of these ranges.

[0088] In an embodiment, at least one surface of the glass article may be contacted with the cleaning composition, such as by immersion in the cleaning composition in an ultrasonic cleaner, for a cleaning duration of about 1 minute to about 60 minutes, such as about 1 min to about 50 min, about 1 min to about 40 min, about 1 min to about 30 min, about 1 min to about 20 min, about 1 min to about 10 min, about 10 min to about 60 min, about 10 min to about 50 min, about 10 min to about 40 min, about 10 min to about 30 min, about 10 min to about 20 min, about 20 min to about 60 min, about 20 min to about 50 min, about 20 min to about 40 min, about 20 min to about 30 min, about 30 min to about 60 min, about 30 min to about 50 min, about 30 min to about 40 min, about 40 min to about 60 min, about 40 min to about 50 min, about 50 min to about 60 min, or any combination of one or more of these ranges.

[0089] Cleaning with the cleaning composition can remove at least a portion of the glass from the surface of the glass article. In an embodiment, cleaning with the cleaning composition can remove less than about 30 nanometers (nm) of glass from the glass surface, such as less than about 20 nm, or less than about 15 nm. In an embodiment, cleaning with the cleaning composition can remove about 1 nm to about 30 nm of glass from the glass surface, such as about 1 nm to about 20 nm, about 1 nm to about 15 nm, about 5 nm to about 30 nm, about 5 nm to about 20 nm, about 5 nm to about 15 nm, or about 10 nm.

[0090] After contacting the glass surface with the cleaning composition, the glass surface can be removed from contact with the cleaning composition, such as by removing the glass surface and / or the glass article from a bath containing the cleaning composition. Removing the glass surface from contact with the cleaning composition can also include rinsing the glass surface and / or the glass article with water at a rinsing temperature (e.g., a temperature above room temperature) and for a certain rinsing time, such as Figure 1 120 in step 120. The water used in the rinsing step 120 can be deionized water. Rinsing the glass surface of the glass article can remove any residual cleaning composition remaining on the glass surface after removal from the cleaning composition bath. Removing the residual cleaning composition on the surface can reduce or prevent further removal of glass from the surface of the glass article.

[0091] In an embodiment, at least one surface may be rinsed with water (such as deionized water) in step 120 for about 1 minute to about 30 minutes, such as about 1 minute to about 25 minutes, about 1 minute to about 20 minutes, about 1 minute to about 15 minutes, about 1 minute to about 10 minutes, about 1 minute to about 5 minutes, about 5 minutes to about 30 minutes, about 5 minutes to about 25 minutes, about 5 minutes to about 20 minutes, about 5 minutes to about 15 minutes, about 5 minutes to about 10 minutes, about 10 minutes to about 30 minutes, about 10 minutes to about 25 minutes, about 10 minutes to about 20 minutes, about 10 minutes to about 15 minutes, about 15 minutes to about 30 minutes, about 15 minutes to about 25 minutes, about 15 minutes to about 20 minutes, about 20 minutes to about 30 minutes, about 20 minutes to about 25 minutes, about 25 minutes to about 30 minutes, or any combination of one or more of these ranges.

[0092] In an embodiment, at least one surface may be rinsed with water, such as deionized water, at step 120 at a temperature of about 35°C to about 95°C, such as about 35°C to about 90°C, about 35°C to about 85°C, about 35°C to about 80°C, about 35°C to about 75°C, about 35°C to about 70°C, about 35°C to about 65°C, about 35°C to about 60°C, about 35°C to about 55°C, about 35°C to about 50°C, about 35°C to about 45°C, about 35°C to about 40°C, about 40°C to about 95°C, about 40°C to about 90°C, about 40°C to about 85°C, about 40°C to about 80°C, about 40 ... ℃, about 40 ℃ to about 70 ℃, about 40 ℃ to about 65 ℃, about 40 ℃ to about 60 ℃, about 40 ℃ to about 55 ℃, about 40 ℃ to about 50 ℃, about 40 ℃ to about 45 ℃, about 45 ℃ to about 95 ℃, about 45 ℃ to about 90 ℃, about 45 ℃ to about 85 ℃, about 45 ℃ to about 80 ℃, about 45 ℃ to about 75 ℃, about 45 ℃ to about 70 ℃, about 45 ℃ to about 65 ℃, about 45 ℃ to about 60 ℃, about 45 ℃ to about 55 ℃, about 45 ℃ to about 50 ℃, about 50 ℃ to about 95 ℃, about 50 ℃ to about 90 ℃, about 50 ℃ to about 85 ℃, about 50 ℃ to about 80 ℃, about 50 ℃ to about 75 ℃ ℃, about 50 ℃ to about 70 ℃, about 50 ℃ to about 65 ℃, about 50 ℃ to about 60 ℃, about 50 ℃ to about 55 ℃, about 55 ℃ to about 95 ℃, about 55 ℃ to about 90 ℃, about 55 ℃ to about 85 ℃, about 55 ℃ to about 80 ℃, about 55 ℃ to about 75 ℃, about 55 ℃ to about 70 ℃, about 55 ℃ to about 65 ℃, about 55 ℃ to about 60 ℃, about 60 ℃ to about 95 ℃, about 60 ℃ to about 90 ℃, about 60 ℃ to about 85 ℃, about 60 ℃ to about 80 ℃, about 60 ℃ to about 75 ℃, about 60 ℃ to about 70 ℃, about 60 ℃ to about 65 ℃, about 65 ℃ to about 95 ℃, about 65 ℃ to about 90 ℃ ℃, about 65 ℃ to about 85 ℃, about 65 ℃ to about 80 ℃, about 65 ℃ to about 75 ℃, about 65 ℃ to about 70 ℃, about 70 ℃ to about 95 ℃, about 70 ℃ to about 90 ℃, about 70 ℃ to about 85 ℃, about 70 ℃ to about 80 ℃, about 70 ℃ to about 75 ℃, about 75 ℃ to about 95 ℃, about 75 ℃ to about 90 ℃, about 75 ℃ to about 85 ℃, about 75 ℃ to about 90 ℃, about 75 ℃ to about 85 ℃, about 75 ℃ to about 80 ℃, about 80 ℃ to about 95 ℃, about 80 ℃ to about 90 ℃, about 80 ℃ to about 85 ℃, about 85 ℃ to about 95 ℃, about 85 ℃ to about 90 ℃, or any combination of one or more of these ranges.

[0093] Reference again Figure 1, the method 100 disclosed herein may include ultrasonically cleaning the surface of the glass article in a bath comprising water in step 130. In an embodiment, the water may be deionized water. During the ultrasonic cleaning process, the glass surface or the entire glass article may be immersed in the water bath. Ultrasonic cleaning can be performed in an ultrasonic parts cleaning machine that is operable to ultrasonically agitate the deionized water bath. Ultrasonic rinsing can be performed at an elevated ultrasonic cleaning temperature (e.g., a temperature above room temperature) and for an ultrasonic cleaning duration. Ultrasonic cleaning can further remove residual reagents on the surface of the glass article. Ultrasonic agitation of the deionized water bath during the ultrasonic cleaning step can help move residual reagents from the surface into the bulk volume of the deionized water bath.

[0094] In an embodiment, ultrasonic cleaning of at least one surface with a cleaning composition may be performed at a frequency of 20Mhz to 80Mhz, such as 20Mhz to 70Mhz, 20Mhz to 60Mhz, 20Mhz to 50Mhz, 20Mhz to 40Mhz, 20Mhz to 30Mhz, 30Mhz to 80Mhz, 30Mhz to 70Mhz, 30Mhz to 60Mhz, 30Mhz to 50Mhz, z, 30Mhz to 40Mhz, 40Mhz to 80Mhz, 40Mhz to 70Mhz, 40Mhz to 60Mhz, 40Mhz to 50Mhz, 50Mhz to 80Mhz, 50Mhz to 70Mhz, 50Mhz to 60Mhz, 60Mhz to 80Mhz, 60Mhz to 70Mhz, 70Mhz to 80Mhz, or any combination of one or more of these ranges.

[0095] In an embodiment, at least one surface may be ultrasonically cleaned with deionized water at about 35°C to about 95°C, for example, about 35°C to about 90°C, about 35°C to about 85°C, about 35°C to about 80°C, about 35°C to about 75°C, about 35°C to about 70°C, about 35°C to about 65°C, about 35°C to about 60°C, about 35°C to about 55°C, about 35°C to about 50°C, about 35°C to about 45°C, about 35°C to about 40°C, about 40°C to about 95°C, about 40°C to about 95°C, about 40°C to about 80°C, about 40°C to about 75°C, about 40°C to about 75°C, about 40°C to about 75°C. 0°C, about 40°C to about 65°C, about 40°C to about 60°C, about 40°C to about 55°C, about 40°C to about 50°C, about 40°C to about 45°C, about 45°C to about 95°C, about 45°C to about 90°C, about 45°C to about 85°C, about 45°C to about 80°C, about 45°C to about 75°C, about 45°C to about 70°C, about 45°C to about 65°C, about 45°C to about 60°C, about 45°C to about 55°C, about 45°C to about 50°C, about 50°C to about 95°C, about 50°C to about 90°C, about 50°C to about 85°C, about 50°C to about 80°C, about 50°C to about 75°C, about 50°C to about to about 70°C, about 50°C to about 65°C, about 50°C to about 60°C, about 50°C to about 55°C, about 55°C to about 95°C, about 55°C to about 90°C, about 55°C to about 85°C, about 55°C to about 80°C, about 55°C to about 75°C, about 55°C to about 70°C, about 55°C to about 65°C, about 55°C to about 60°C, about 60°C to about 95°C, about 60°C to about 90°C, about 60°C to about 85°C, about 60°C to about 80°C, about 60°C to about 75°C, about 60°C to about 70°C, about 60°C to about 65°C, about 65°C to about 95°C, about 65°C to about 90°C, ℃ to about 65 ℃ to about 85 ℃, about 65 ℃ to about 80 ℃, about 65 ℃ to about 75 ℃, about 65 ℃ to about 70 ℃, about 70 ℃ to about 95 ℃, about 70 ℃ to about 90 ℃, about 70 ℃ to about 85 ℃, about 70 ℃ to about 80 ℃, about 70 ℃ to about 75 ℃, about 75 ℃ to about 95 ℃, about 75 ℃ to about 90 ℃, about 75 ℃ to about 85 ℃, about 75 ℃ to about 80 ℃, about 80 ℃ to about 95 ℃, about 80 ℃ to about 90 ℃, about 80 ℃ to about 85 ℃, about 85 ℃ to about 95 ℃, about 85 ℃ to about 90 ℃, or any combination of one or more of these ranges.

[0096] In an embodiment, at least one surface may be ultrasonically cleaned with deionized water for about 1 minute to about 30 minutes, such as about 1 minute to about 25 minutes, about 1 minute to about 20 minutes, about 1 minute to about 15 minutes, about 1 minute to about 10 minutes, about 1 minute to about 5 minutes, about 5 minutes to about 30 minutes, about 5 minutes to about 25 minutes, about 5 minutes to about 20 minutes, about 5 minutes to about 15 minutes, about 5 minutes to about 10 minutes, about 10 minutes to about 30 minutes, about 10 minutes to about 25 minutes, about 10 minutes to about 20 minutes, about 10 minutes to about 15 minutes, about 15 minutes to about 30 minutes, about 15 minutes to about 25 minutes, about 15 minutes to about 20 minutes, about 20 minutes to about 30 minutes, about 20 minutes to about 25 minutes, about 25 minutes to about 30 minutes, or any combination of one or more of these ranges.

[0097] After ultrasonic cleaning, the glass surface and / or glass article can be removed from the deionized water bath used for ultrasonic cleaning. Figure 1 In an embodiment, method 100 may further include drying the surface of the glass article in step 140. In an embodiment, the drying step 140 may be performed after the ultrasonic cleaning step 130 and after the glass article is removed from contact with the ultrasonic deionized water bath. In an embodiment, the drying step may be performed in an inert atmosphere (such as an atmosphere containing an inert gas). The inert gas may include, but is not limited to, nitrogen, a rare gas (helium, neon, argon, krypton, etc.), or a combination thereof. In an embodiment, the surface of the glass article may be dried under a nitrogen stream. After the drying step 140, the glass article may be stored in a clean room until use. Storage in a clean room can reduce the accumulation of contaminants on the glass surface during storage.

[0098] In an embodiment, after the cleaning step 110, the glass article may be stored in a deionized water bath, which may reduce subsequent particle deposition caused by contact between the glass surface and air. In an embodiment, before the glass article is immersed in deionized water for storage, the surface of the glass article may be rinsed with deionized water in step 120, ultrasonically cleaned with deionized water in step 130, or both.

[0099] The cleaning compositions and methods disclosed herein can be used to clean glass articles produced from glass substrates. Non-limiting examples of suitable commercially available glass substrates include, but are not limited to, EAGLE LOTUS TM , POLARCOR TM and Glass, including chemically strengthened, chemically tempered and / or thermally tempered versions thereof. The glass cleaning compositions and methods can be used to clean glass articles used in electronic devices, optical systems, or other glass applications that require glass surface contamination. In embodiments, the glass cleaning compositions and methods herein can be used to clean glass disks containing Lotus™ glass used in the production of hard disk components for electronic devices. In embodiments, the cleaning compositions and methods can be used to clean POLARCOR TM Polarized glass components and other applications.

[0100] Example

[0101] Various embodiments of the coated glass articles disclosed herein will be further illustrated by the following examples. The examples are illustrative in nature and should not be construed as limiting the subject matter of the present disclosure.

[0102] Example 1: Cleaning Glass Dishes of Organic Contaminants

[0103] In Example 1, the cleaning composition according to the present disclosure is used to remove organic contaminants on the surface of a glass product. For Example 1, the glass product is a glass disk produced for a hard disk product for a computer. The glass of Example 1 is LOTUS 100 from Corning. TM NXT Glass. Reference now Figure 5 , schematically depicts a general process 500 for producing the glass disks of Example 1. The manufacturing process 500 generally includes providing a glass sheet 501 and laser cutting 502 the glass sheet 501 to produce a glass disk 503. The glass disks are then transferred using a robot arm 504 and stacked into a stack 506, wherein the glass disks are separated by backing paper 508. Therefore, during the manufacturing process, the glass disks contact the robot arm and the backing paper, and through this contact, the glass disks can be contaminated by various organic contaminants.

[0104] The glass pieces were disassembled, removed from the stack, and analyzed for organic contaminants using thermal desorption gas chromatography (GC), mass spectrometry (MS), and UHPLC mass spectrometry (UHPLC-MS) methods according to known test methods. In order to evaluate the glass pieces using thermal desorption gas chromatography and / or mass spectrometry, a thermal desorption module from Gerstel Inc. was coupled to a Hewlett-Packard GC / MS system (HP 5971GC, Agilent 5975MS). In the experiment, each single glass sample holder was checked for background before use. The disc-shaped sample glass pieces were placed in the background-checked sample holder and subjected to the Gerstel thermal desorption system. The device was rapidly heated at a rate of 60°C / min to a final temperature of 400°C and maintained at 400°C for 15 minutes before injection into the GC. The GC was heated at 50°C for 3 minutes, heated to 325°C at a rate of 10°C / min, and maintained at the final temperature for 5 minutes. The purified eluate from the GC column was analyzed by electron impact ionization mass spectrometry. The masses measured range from 41 to 600 atomic mass units (amu).

[0105] To analyze glass disks using ultra-high performance liquid chromatography-mass spectrometry, this application used an Agilent 1292 Infinity II UHPLC interfaced to an Agilent 6560 ion mobility-quadrupole-time of flight (IM-Q-TOF) mass spectrometer with electrospray ionization. A 10 microliter (μL) aliquot of the methanol extraction of the disk sample was injected into a Waters Cortecs C18, 2.7-micron, 2.1X 100mm column using the following gradient: from 80:20 acetonitrile-water to 100% acetonitrile in 5 minutes, and a test run was performed over a 35 minute acquisition time. The eluent peak was analyzed by IM-Q-TOF. The results of the analysis of organic contaminants on the glass surface of the glass disk are provided in Table 1.

[0106] In Example 1, a glass disk having organic contaminants thereon was subjected to Figure 1 The cleaning composition of Example 1 is an aqueous solution comprising 80% by volume of a 14.8M phosphoric acid (H3PO4) solution, 5% by volume of a 15.9M HNO3 solution, 5% by volume of a 17.45M acetic acid (glacial acetic acid) solution, and the remainder of water (10% by volume of supplementary water added). Thus, the cleaning composition comprises 11.84M H3PO4, 0.795M HNO3, and 0.8725M acetic acid in water. Unless otherwise specified, Figure 1 The steps in the method are carried out at the same temperature, duration and ultrasonic stirring settings for each step for all examples and comparative examples presented herein. Specifically, for Example 1, Figure 1The cleaning step 110 is performed at a temperature of 65° C. and lasts for 20 minutes. Figure 1 After cleaning the glass disk of Example 1 with the cleaning composition according to the method in, the organic contaminants on the surface of the glass disk of Example 1 were analyzed using GC, MS and UHPLC-MS, as described above. The results are provided in Table 1.

[0107] Comparative Example A: Cleaning of organic contaminants using conventional cleaning agents

[0108] In Comparative Example A, a conventional cleaning agent was used to clean the glass disk manufactured for hard disks and described in Example 1. For Comparative Example A, the conventional cleaning agent was a 4 wt % PK-LCG225X cleaning solution from Parker Corporation (hereinafter referred to as "Parker cleaning agent"). The glass disk of Comparative Example A was cleaned according to the same process as in Example 1, except that Parker cleaning agent was used in the cleaning step 110. The temperature, time, ultrasonic agitation setting, etc. were the same as those used in Example 1 (i.e., a temperature of 65° C. and a cleaning time of 20 minutes for the cleaning step 110). After the cleaning process, the organic contaminants on the surface of the glass disk of Comparative Example A were analyzed using GC, MS, and UHPLC-MS, as described above. The results are provided in Table 1.

[0109] Comparison of Example 1 and Comparative Example A

[0110] Table 1 below provides the organic contaminants identified on the surface of the glass disks and the concentrations of these contaminants before and after the cleaning process.

[0111] Table 1

[0112]

[0113] In Table 1, dipropylene glycol, dibutyl sebacate, palmitamide, and undecylenic acid were not initially detected on the glass sample surface but were present after cleaning. It is believed that these compounds are environmental contaminants and additives in plastics used in the cleaning process, which may have been introduced into the water and cleaning solution during the cleaning process and subsequently deposited on the glass surface in small amounts.

[0114] For hexaethylene glycol present on the glass surface before cleaning, C9H 23 N2O3、C 18 H 26 N2O7, dibutyl phthalate, C 19 H 43 N3O6、C 21 H 25N3O4, 2-butoxyethyl 4-(dimethylamino)benzoate, and erucamide, which were removed in greater amounts by the cleaning composition of Example 1 compared to cleaning with the conventional cleaning agent of Comparative Example A. As shown in Table 1, the cleaning composition of Example 1 performed as well or better than the conventional cleaning agent of Comparative Example A in removing organic contaminants from glass plates.

[0115] Example 2: Comparison of cleaning composition with conventional cleaning composition

[0116] In Example 2, cleaning of glass plates with the cleaning composition of Example 1 was compared with cleaning with various other conventional glass cleaners to compare changes in glass surface morphology. The glass plates before cleaning were the same as those described in Example 1 and had the organic contaminants listed in Table 1. The cleaning composition of Example 2 was the same as the cleaning composition prepared in Example 1 (e.g., 80% by volume of 14.8M phosphoric acid (H3PO4) solution, 5% by volume of 15.9M HNO3 solution, 5% by volume of 17.45M acetic acid (glacial acetic acid) solution, and the balance of water).

[0117] The cleaning composition of Example 2 was compared with various other conventional glass cleaners such as alkaline pH cleaners, neutral pH cleaners, other acidic pH cleaners, and fluorinated acids (Comparative Examples A to P). The conventional cleaners for Comparative Examples A to P are provided in Table 2. As previously discussed, Comparative Example A is the Parker cleaner of Comparative Example A. The conventional cleaner for Comparative Example B is SEMICLEAN GLASS CLEARING AG, obtained from Yokohama Oils & Fats. TM KG glass cleaner. For Comparative Example C, TMAH refers to tetramethylammonium hydroxide. The SC1 cleaner of Comparative Example D is made of NH4OH (28%), H2O2 (30%) and deionized water in a volume ratio of 1:1:5. The conventional cleaner of Comparative Example H is a 4 wt% solution produced by Valtech Cleaner. The SC2 cleaner of Comparative Example K was prepared by mixing HCl (37%), H2O2 (30%), and deionized water in a volume ratio of 1:1:5.

[0118] according to Figure 1The glass plates were cleaned using the cleaning composition of Example 2 and the conventional glass cleaner of Comparative Examples A to P according to the method in Example 2. Each of Example 2 and Comparative Examples A to M used the same operating conditions of the cleaning method. Due to the aggressiveness of the fluorine compounds used to dissolve the glass, the cleaning temperature and cleaning duration of Comparative Examples N, O and P were reduced. The cleaning temperature, cleaning time and cleaning pH are provided in Table 2. After cleaning, the particle count and glass surface roughness were measured by Zetascan analysis and atomic force microscopy (AFM) analysis, respectively. In general, AFM is able to characterize the feature size on the glass surface with a spatial resolution of about 10 nm. The results are provided in Table 2. For each sample, the surface roughness on an area of ​​2 microns by 2 microns square was measured and the average value was taken. Using a FastScan-B probe, a Bruker Dimension Atomic force microscopy (AFM) analysis was performed.

[0119] The surface scanning inspection system (SSIS) is the most commonly used instrument for high-speed inspection of surface cleanliness in the semiconductor and large panel display (LPD) industries. For Example 2, the SSIS system used to inspect the glass samples tested was the ZETASCAN from KLA-Tencor. TM 800SSIS.ZETASCAN TM The 800 system is a high-throughput defect inspection and classification system based on lasers (laser with 405nm wavelength and 150mW power). The system is equipped with 4 simultaneous collection channels, which can accurately classify multiple defect types (particles, pits, scratches, etc.) on a variety of substrates including rough ground, polished, unpolished, opaque, translucent and transparent materials. ZETASCAN TM The 800 has a sample 2D spatial resolution of 10um / pixel and can detect particles larger than 300nm, with good A / B separation for glass substrates thicker than 0.3mm. Each glass sample is supported by multiple magnetic pins and attached to an XYZ stage.

[0120] The received glass disks were not pre-cleaned after laser cutting and packaging. For most contaminants, the total surface contamination level exceeded the ZETASCAN TM The maximum countable level of the 800 system (200,000) caused the analysis to fail. With fewer reference points, comparing particle removal efficiency and particle size distribution (PSD) became a challenge for the pre-cleaning process. To evaluate the performance of different chemistries after pre-cleaning, instead of using PSD, the contamination density (counts / area) of particles smaller than 100um was used. Finally, the PSD between the two best cleaning chemistries was compared to provide better process understanding.

[0121] For beyond ZETASCAN TM The 800 system detects a wide range of surface contamination, converting 16-bit raw data into digital images for qualitative evaluation. These images are extremely helpful for pre-clean evaluation, visualizing contamination issues above measurable levels. Data analysis scripts can be deployed to classify multiple types of defects with unique characteristics: such as top particles with double peaks, scratches with large aspect ratios, pits with top scattering area larger than side scattering, etc. In addition, data analysis areas are defined to remove scattered noise from the edge of the wafer. The annular analysis area is used for glass disks, which represent hard disk substrates.

[0122] ZETASCAN TM The 800 instrument is placed in a Class 100 clean room to minimize secondary contamination from the air. Minimize contact with the sample during measurement to reduce surface scratches and particle contamination caused by handling. Specifically, a special hook is used to extract and return the sample by only touching the inner edge of the wafer. At the same time, an empty slot is left between each glass plate to reduce collision between glass plates.

[0123] Table 2

[0124]

[0125] Among a large number of cleaning agents and fluoric acid in the acidic pH to alkaline pH range, the top three that performed best in terms of particle density on the glass surface after cleaning were the conventional alkaline cleaning agents of Comparative Examples A and B and the cleaning composition of Example 2. However, compared to the alkaline cleaning agents of Comparative Examples A and B, the cleaning composition of Example 2 removed less glass material from the glass surface and maintained the surface roughness at a lower level after cleaning.

[0126] The PNA cleaning composition of Example 2 provides similar performance in removing organic contaminants compared to conventional cleaning compositions. Alkaline cleaners are the best in removing organic contaminants. The PNA cleaning composition of Example 2 shows the closest performance to the basic cleaner.

[0127] Example 3: Cleaning wet inorganic particles with a cleaning composition

[0128] In Example 3, the cleaning compositions disclosed herein of inorganic particles for cleaning glass surfaces while the inorganic particles and the glass surface are still wet from a polishing operation were evaluated. For Example 3, three different types of CeO particles from two different suppliers (CeO from Ferro Corporation) were used. x Pellets; MIREK from Mitsui Kinzoku, Tokyo, Japan TM E CeO2 particles; and MIREK also from Mitsui KinzokuTM HL CeO2 particles) were used to edge polish the glass disk described in Example 1. The CeO2 particles and polishing pH for each sample of Example 3 are provided in Table 3. After edge polishing with CeO2 particles, the cleaning composition of Example 1 (e.g., 80 volume % of 14.8M phosphoric acid (H3PO4) solution, 5 volume % of 15.9M HNO3 solution, 5 volume % of 17.45M acetic acid (glacial acetic acid) solution and the balance of water) was then used according to Figure 1 The polished glass disk of Example 3 was cleaned by the method described in while keeping the CeO2 particles in a wet condition.

[0129] Comparative Examples Q and R

[0130] In Comparative Examples Q and R, inorganic particles were cleaned from the glass surface with two conventional glass cleaners while the inorganic particles and the glass surface were still wet due to the polishing operation. For Comparative Examples Q and R, the glass disks described in Example 1 were edge polished with three different types of CeO2 particles as described in Example 3. The CeO2 particles and polishing pH for each sample of Comparative Examples Q and R are provided in Table 3. After edge polishing with CeO2 particles, the inorganic particles and the glass surface were then polished according to Figure 1 Each polished glass disk of Comparative Examples Q and R was cleaned with a conventional glass cleaner while keeping the CeO2 particles in a wet condition. For Comparative Example Q, the conventional cleaner was Parker cleaner (i.e., For Comparative Example R, the conventional detergent was 5 wt % of Detergent solution, which is a neutral pH detergent.

[0131] Table 3

[0132]

[0133]

[0134] Comparison of Example 3 with Comparative Examples Q and R

[0135] The particle density of CeO2 particles remaining on the front surface of the cleaned glass disks of Example 3 and Comparative Examples Q and R (front particle density) was evaluated according to the methods provided herein (e.g., AFM analysis and Zetascan). Multiple cleaned glass disks were measured for each sample in each of Example 3 and Comparative Examples Q and R. The particle density is provided graphically in Figure 6 and are provided numerically in Table 4. Figure 6Regardless of the pH of the CeO2 slurry or the type of CeO2 particles used for polishing, the cleaning composition of Example 3 (Samples 3-1 to 3-6) showed the best cleaning results compared to the conventional alkaline and neutral pH glass cleaners of Comparative Examples Q and R. It is noted that for Comparative Examples R-4, Q-5, and R-6, the particle count values ​​exceeded the upper detection limit of the test method and instrument and were therefore not included in the Table of Contents. Figure 6 Available in.

[0136] Table 4

[0137]

[0138]

[0139] Reference now Figures 7 to 9 , Example Q-1( Figure 7 ), Comparative Example R-1( Figure 8 ) and Example 3-1( Fig. 9 ) of the front surface of a clean glass disk, where all polishing pH was 7. Figures 7 to 9 In the figure, the white area indicates the presence of cerium dioxide particles on the front surface of the glass disk. Fig. 9 It can be seen that compared with Comparative Example Q-1 ( Figure 7 ) and Comparative Example R-1( Figure 8 ), the glass plate of Example 3-1 cleaned with the cleaning composition disclosed herein showed less evidence of cerium dioxide particles.

[0140] Reference now Figures 10 to 12 , Example Q-2 ( Fig.10 ), Comparative Example R-2 ( Fig.11 ) and Example 3-1( Fig.12 ) of the front surface of a clean glass disk, where all polishing pH was 9. Figures 10 to 12 In the figure, the white area indicates the presence of cerium dioxide particles on the front surface of the glass disk. Fig.12 It can be seen that compared with Comparative Example Q-2 ( Fig.10 ) and Comparative Example R-2( Fig.11 ), the glass plate of Example 3-2 cleaned with the cleaning composition disclosed herein showed less evidence of cerium dioxide particles. Figures 7 to 12 It is clearly shown that the cleaning compositions disclosed herein are more effective in removing wet CeO 2 particles from the surface of the glass article after polishing with CeO 2 , regardless of the pH of the polishing step.

[0141] The polished and cleaned disks of Examples 3-1 and 3-2 and Comparative Examples Q-1, Q-2, R-1 and R-2 were analyzed using energy dispersive X-ray (EDX) spectroscopy to determine the CeO2 content (wt%) on the glass disk surface. The Oxford energy dispersive X-ray spectrometer was attached to a Hitachi SU5000 scanning electron microscope (SEM). SEM images were acquired at 15KV using a back-emitting detector, and the chemical composition was analyzed by EDX-SEM at 15KV, and the spot size in the acquisition software was set to 50. The EDX spectrum was taken perpendicular to the glass surface. The working principle of EDX-SEM is as follows: the material is excited by the electron beam of the electron microscope, and then some of the absorbed energy is dissipated by ejecting core-shell electrons. Then, the higher energy shell electrons continue to fill their positions, releasing energy differences in the form of X-rays, which have characteristic spectra based on their origin atoms. This allows for composition analysis of a given sample volume excited by an electron beam. The position of the peak in the spectrum identifies the element, and the signal intensity corresponds to the concentration of the element. The results are reported in Table 5. As shown in Table 5, the results show that CeO2 particles were effectively removed from the glass surface using the acidic cleaning composition disclosed herein (Example 3). Further increasing the CeO2 slurry pH from 7 to 9 improved the performance of the alkaline and neutral pH detergents of Comparative Examples Q and R, but the results of the acidic cleaning composition of Example 3 were still superior.

[0142] Table 5

[0143]

[0144] As previously discussed, increasing the pH of the polishing step can further improve the performance of the cleaning composition of Example 3 in removing CeO2 particles. Fig.13 , graphically depicts the pre-particle density measured for Examples 3-1 to 3-6. The pre-particle density was determined according to the test method disclosed herein. Fig.13 As shown, increasing the pH of the polishing step from 7 to 9 reduces the particle count on the glass surface after cleaning with the cleaning composition of Example 3.

[0145] Reference now Fig.14 , graphically showing the front particle density of the cleaned glass disks of Example 3-2 and Comparative Examples Q-2 and R-2. Fig.14It can be seen that when polishing at a high pH of 9, the cleaning composition of Example 3-2 results in a lower pre-particle density than the conventional cleaners of Comparative Examples Q-2 (alkaline pH cleaner) and R-2 (neutral pH cleaner). Without being bound by any particular theory, it is believed that the high pH of the CeO2 particles anchors the negative ions on the surface of the particles and prevents them from aggregating. When the CeO2 particles come into contact with the cleaning composition of Example 3-2, the acidic cleaning composition of Example 3-2 grabs the CeO2 particles faster than the conventional cleaning composition due to electrostatic forces, which may induce particle agglomeration and precipitation of CeO2 agglomerates to be removed from the cleaning solution. It is believed that the agglomeration and precipitation of CeO2 particles leads to the better cleaning efficiency of the cleaning composition of Example 3.

[0146] Of the three factors that determine the cleaning efficiency of a cleaning agent (e.g., solvency, charge interaction with the contaminants to be removed, and tendency to leave residues after water rinsing), charge interaction is believed to play an important role in the cleaning efficiency of the cleaning compositions herein. The zeta potential of the pre-treated CeO2 slurry, the cleaning composition of Example 3, and the conventional cleaning agents of Comparative Examples Q and R were measured before and after cleaning.

[0147] Zeta potential (ZP) and pH characterization measurements were run on a Malvern Zetasizer Nano ZS90 instrument equipped with a 633nm wavelength laser using a combination of measurement techniques (i.e., electrophoresis and laser Doppler velocimetry). The method measures the speed at which colloidal particles move through a fluid due to an applied electric field that determines electrophoretic mobility. The zeta potential is calculated using Henry's equation at speed and electric field strength and other known constants (viscosity and dielectric constant) of the fluid / particle system.

[0148] The particle size range of the characterized powders is from 4nm to about 10+μm. The sample amount required is very small, typically about 10μL of slurry sample is required for every 10-25mL electrolyte dispersant (nominal 10mM KCl aqueous solution). Each individual sample is prepared in a pH range of about 2 to 12. Electrolyte dispersants of 4 separate pH values ​​are prepared by adjusting the pH value to lower and higher pH values ​​using HCl and KOH solutions, respectively. The zeta potential of these samples is then evaluated (measured three times) to construct an overall ZP vs. pH curve, thereby obtaining a graphical measurement result to visualize the pH sensitivity of the material. Table 6 summarizes the zeta potential data for CeO2 slurry, the cleaning composition of Example 3, and the conventional cleaning agents of Comparative Examples Q and R.

[0149] Table 6

[0150]

[0151] The more negative the zeta potential value, the more stable the CeO2 particles are in solution. When the CeO2 particles are in contact with the acidic cleaning composition of Example 3, the zeta potential drops rapidly. Without being bound by any particular theory, it is believed that the rapid drop in zeta potential observed for the cleaning composition of Example 3 may be attributed to the CeO2 particles on the glass surface being quickly attracted by the reagent molecules of the cleaning composition of Example 3 due to electrical interactions, and then the CeO2 particles form agglomerates. Due to the low zeta potential, the CeO2 particles are relatively stable in solution, and then the formed CeO2 agglomerates precipitate out and prevent the CeO2 particles from reattaching to the glass surface.

[0152] Reference now Fig.15 , graphically depicts the zeta potential of the pre-accepted CeO2 slurry, the cleaning compositions of Examples 3-1 to 3-6 after cleaning, and the conventional cleaning agents of Comparative Examples Q-1 to Q-6 and R-1 to R-6 after cleaning. Fig.15 As shown, the zeta potentials of the cleaning compositions of Examples 3-1 to 3-6 have the smallest zeta potential magnitudes.

[0153] Reference now Fig.16 , graphically depicts the zeta potential (y-axis) of various CeO2 particles as a function of pH (x-axis) after polishing at pH 7 and pH 9. At pH values ​​below 4, the CeO2 particles precipitate too quickly to accurately measure the pH of the particles and are therefore not measured at pH 7. Fig.16 As shown in Fig.16 As shown, the magnitude of the zeta potential of CeO2 particles increases to a maximum at a pH of about 10 (e.g., since the zeta potential is negative, the maximum magnitude of the zeta potential is Fig.16 The minimum value in the figure). Fig.16 This indicates that better cleaning efficiency can be achieved at lower pH. Specifically, since precipitation occurs rapidly at pH values ​​below 4, it is believed that such precipitation at pH values ​​below 4 can improve cleaning efficiency by reducing or preventing CeO2 particles from redepositing on the surface.

[0154] Ferro CeO2 particles of a fixed mass per unit volume are added to the cleaning composition of Example 3 and various conventional cleaning agents of Comparative Examples Q and R. The mixture is stirred for a period of time. For each mixture, stirring is stopped at the end of the time period, and the mass of the precipitate is measured at the end of the stirring time period. The mass of the precipitate is measured as a function of time. During the measurement, it was observed that the CeO2 particles in the cleaning composition of Example 3 precipitated too quickly, and most of the precipitates precipitated before the mass measurement was started. Therefore, it was found that the acidic pH of the cleaning composition of Example 3 caused a faster precipitation rate of CeO2 particles compared with the alkaline pH conventional cleaning agent of Comparative Example Q or the neutral pH conventional cleaning agent of Comparative Example R. As previously discussed, it is believed that this faster precipitation rate of the acidic cleaning composition of Example 3 can improve cleaning efficiency by reducing or preventing CeO2 particles from being re-deposited on the glass surface.

[0155] Example 4: Effectiveness of the disclosed cleaning composition in cleaning dry inorganic particles

[0156] In Example 4, the cleaning compositions disclosed herein are demonstrated to be effective in cleaning dried CeO2 particles on the surface of polished glass articles. When CeO2 particles are dried on the glass surface, it becomes more difficult to remove CeO2 particles than when CeO2 particles are removed in wet conditions. The acidic cleaning compositions disclosed herein can also effectively clean dried CeO2 particles on the surface of glass articles. For Example 4, a POLARCOR 1000 from Corning Corporation was included. TM Glass test pieces of glass are used as glass products. Fig.17 , shows a line scan dark field scattering image of a glass coupon surface before CeO2 particles are applied to the coupon surface.

[0157] The glass coupons were sprayed with a diluted CeO2 slurry in 18M ohm DI water using a 2 fluid ounce (oz. or approximately 60 mL) fine mist spray bottle. The CeO2 slurry was provided by the contract manufacturer (CM) polisher and is the same slurry they use to polish POLARCOR from Corning. TM The same as the glass product. The D50 particle size of the CeO2 particles was measured to be between about 0.4 μm and about 0.6 μm. The sprayed CeO2 slurry was allowed to dry on the surface of the glass product. Now refer to Fig.18 , after applying CeO2 particles, provides a line scan dark field scattering image of the glass coupon surface. Fig.18 As shown, white spots indicate the presence of dried CeO2 slurry.

[0158] After drying, the cleaning composition of Example 1 (e.g., 80% by volume of a 14.8M phosphoric acid (H3PO4) solution, 5% by volume of a 15.9M HNO3 solution, 5% by volume of a 17.45M acetic acid (glacial acetic acid) solution, and the balance of water (10% by volume of supplementary water added)) was then used according to Figure 1 The surface of the glass specimen was cleaned by the method described in Fig.19 , shows a line scan dark field scattering image of the surface of a glass test piece after cleaning with the cleaning composition of Example 1. Fig.19 As shown, the cleaning composition of Example 1 removed all visible signs of dried CeO2 particles on the surface of the glass coupon. Therefore, the cleaning composition of Example 1 showed good cleaning efficiency for removing dried CeO2 particles.

[0159] The surface roughness of the glass sample surface before and after cleaning was measured by a Zygo meter. The results are provided in Table 7. As shown in Table 7, cleaning with the cleaning composition of Example 1 has no significant effect on the surface roughness of the glass test piece.

[0160] Table 7

[0161]

[0162] In addition, after the cleaning process using the cleaning composition of Example 1, the glass coupons met the polarization specifications of the specific product both after cleaning and after the final thermochemical reduction process. The results of transmittance, contrast ratio and polarization angle are provided in Table 8. The optical properties of control samples, glass discs sprayed with CeO2 slurry and then cleaned with the cleaning composition, and samples obtained from a contract manufacturer were evaluated using a Polarcor optical polarizer. The transmittance on the fast axis should be above 90%, and the contrast ratio describes the ratio between the transmission in the desired polarization direction and the undesired orthogonal polarization direction, which is typically above one million. The experimental results in Table 8 show that the optical specifications of the final glass product are not affected by chemical cleaning with the cleaning composition disclosed herein.

[0163] Table 8

[0164]

[0165] While various embodiments of cleaning compositions and methods for cleaning glassware surfaces have been described herein, it should be understood that it is contemplated that each of these embodiments and techniques can be used alone or in combination with one or more embodiments and techniques.

[0166] It will be apparent to those skilled in the art that various modifications and changes may be made to the embodiments disclosed herein without departing from the spirit and scope of the claimed subject matter. Therefore, this specification is intended to cover modifications and changes of the various embodiments described herein, as long as such modifications and changes are within the scope of the appended claims and their equivalents.

Claims

1. A method for manufacturing a glass product, the method comprising: cleaning at least one surface of the glass article, wherein the at least one surface of the glass article comprises organic contaminants, inorganic particles, or both deposited on the at least one surface, and cleaning the at least one surface of the glass article comprises contacting the at least one surface with a cleaning composition comprising: About 0.4 mol / L to about 1.7 mol / L HNO3; From about 0.5 mol / L to about 1.8 mol / L acetic acid; and About 6.0 mol / L to about 14.0 mol / L of phosphoric acid, wherein the phosphoric acid is an acid having at least one phosphoric acid functional group.

2. The method of claim 1, wherein cleaning the at least one surface comprises: ultrasonically cleaning the at least one surface of the glass article with the cleaning composition; flushing the at least one surface with water; ultrasonically cleaning the at least one surface with water; and The at least one surface is dried under an inert atmosphere.

3. The method of claim 2, comprising ultrasonically cleaning the at least one surface with the cleaning composition at a frequency of about 20 Mhz to about 80 Mhz.

4. The method of any one of claims 2 or 3, comprising ultrasonically cleaning the at least one surface with the cleaning composition for about 1 minute to about 60 minutes.

5. The method of any one of claims 2-4, comprising ultrasonically cleaning the at least one surface with the cleaning composition at a temperature of about 35°C to about 95°C.

6. The method of any one of claims 2-5, comprising flushing the at least one surface with water for about 1 minute to about 30 minutes.

7. The method of any one of claims 2-6, comprising flushing the at least one surface with water at a temperature of about 35°C to about 95°C.

8. The method of any one of claims 2-7, comprising ultrasonically cleaning the at least one surface with water for about 1 minute to about 30 minutes.

9. A method as claimed in any one of claims 2 to 8, comprising ultrasonically cleaning the at least one surface with water at a temperature of 35°C to 95°C.

10. The method of any one of claims 1-9, wherein the inert atmosphere comprises nitrogen.

11. The method of any one of claims 1-10, wherein the at least one surface of the glass article after cleaning is removed to a depth of about 1 nm to about 20 nm.

12. The method of any one of claims 1-11, wherein the removal depth of the at least one surface of the glass article after cleaning is less than or equal to 20 nm, less than or equal to 10 nm, less than or equal to 7 nm, or even less than or equal to 4 nm.

13. The method of any one of claims 1-12, wherein the surface roughness of the at least one surface of the glass article increases by less than or equal to 10% after cleaning.

14. The method of any one of claims 1-13, wherein the surface roughness of the at least one glass surface increases by less than or equal to 5% after cleaning.

15. The method of any one of claims 1-14, further comprising forming the glass article, wherein: forming the glass article comprises polishing the at least one surface of the glass article with CeO2 particles; and The polishing results in residual CeO 2 particles adhered to the at least one surface of the glass article.

16. The method of claim 15, wherein the residual CeO2 particles are dry on the at least one surface of the glass article when the at least one surface is contacted with the cleaning composition.

17. The method of any one of claims 15 or 16, wherein after cleaning the at least one surface, the amount of CeO2 particles on the at least one surface of the glass article is less than or equal to 600 particles / cm 2 .

18. The method of any one of claims 1 to 17, wherein the phosphoric acid is selected from H3PO4, H4P2O7, H5P3O 10 and organophosphates.

19. The method of any one of claims 1-18, wherein the phosphoric acid is H3PO4.

20. The method of any of claims 1-19, wherein the cleaning composition has a pH of about -3 to about -1.

21. The method of any one of claims 1-20, wherein the cleaning composition does not contain a fluorine-containing compound.

22. The method of any one of claims 1-21, wherein the cleaning composition comprises about 0.6 mol / L to about 0.9 mol / L HNO3.

23. The method of any one of claims 1-22, wherein the cleaning composition comprises about 0.7 mol / L to about 1.0 mol / L acetic acid.

24. The method of any one of claims 1-23, wherein the cleaning composition comprises about 7.0 mol / L to about 14.0 mol / L or about 9.0 mol / L to about 13.0 mol / L of the phosphoric acid.

25. The method of any one of claims 1-24, wherein the cleaning composition consists essentially of: An aqueous solution consisting essentially of: About 0.4 mol / L to about 1.7 mol / L HNO3; about 0.5 mol / L to about 1.8 mol / L acetic acid; From about 6.0 mol / L to about 14.0 mol / L H3PO4; and Remaining amount of water.

26. The method of any one of claims 1-25, wherein the cleaning composition consists essentially of: An aqueous solution consisting essentially of: About 0.6 mol / L to about 0.9 mol / L HNO3; about 0.7 mol / L to about 1.0 mol / L acetic acid; From about 9.0 mol / L to about 14.0 mol / L H3PO4; and Remaining amount of water.

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