TW201504177A - Methods of treating glass surfaces - Google Patents

Abstract

Disclosed herein are methods for treating an etched glass surface comprising applying a cleaning solution comprising at least one mineral acid to a glass substrate that has been etched. Also disclosed herein is a cleaning solution comprising at least one mineral acid for cleaning a glass substrate that has been etched.

Description

Method of treating a glass surface [Cross-reference to related applications]

The present patent application claims priority to U.S. Provisional Patent Application Serial No. 61/858,292, filed on Jul. 25, 2013, the content of which is hereby incorporated by reference in its entirety Incorporating this document is as fully described below.

Disclosed herein is a method for treating an etched glass surface, the method comprising applying a solution comprising at least one mineral acid to the etched glass surface. In at least some embodiments, the glass surface has been etched using an etchant comprising fluoride ions. In certain embodiments, the solution comprising at least one mineral acid is free of fluoride ions. Also disclosed herein are solutions for treating an etched glass surface comprising at least one mineral acid. In certain exemplary embodiments, the cleaning solution is free of fluoride ions. Further disclosed herein is an etched glass surface that has been prepared by a process comprising applying a solution containing at least one mineral acid to the surface of the etched glass, etched using an etchant comprising fluoride ions.

In the manufacture of glass panels, it is common to thin (ie etch) glass panels, for example after assembling an LCD module. For example, you can use Hydrofluoric acid (HF) thins the glass panel to a range of substrate thicknesses from about 0.1 mm to about 0.4 mm. However, the thinning or etching process may result in insoluble by-products that are conventionally known as sludge. The sludge is produced from the etching process and adheres to the glass surface, contaminating the glass. The glass panel can be cleaned and/or removed from the glass panel after etching the glass panel by physical or chemical means, or both.

For example, a glass panel can be brushed after etching. However, brushing can cause damage to the glass surface, which may result in a decrease in the strength and surface quality of the glass. In a physical brushing process, the previously etched glass can be rinsed first in a water rinse and then brushed. When the contaminant is soluble in water, a simple water rinse may have an effect. However, when contaminants on the surface of the glass have poor solubility in water and/or strong adhesion to the surface of the glass, brushing is often used. However, scrubbing not only removes contaminants from the glass surface, but also introduces scratches or defects onto the glass surface. Scratches or defects can significantly reduce the strength and performance of the glass, even if the shape of the defect is small and/or shallow.

Another method of cleaning the surface of the etched glass is by chemical cleaning. Chemical cleaning can overcome some of the limitations of physical cleaning methods. In chemical cleaning, the rinsing liquid is not water, but a solution that removes sludge from the surface of the glass, and may not require brushing when using chemical cleaning.

During the chemical cleaning process, the dirty contaminated glass surface (which has been etched by the etchant solution) is treated, and theoretically a new, clean, non-contaminating surface is created. Under ideal theoretical conditions, contaminants fall off the etched surface and do not reattach to the regenerated clean surface; however, It should be appreciated that contaminants that are detached from the glass surface during the etching process may reattach to the etched glass surface, resulting in re-contaminated etched glass. Nevertheless, chemical cleaning is used to clean (ie, process) the glass surface. Both alkaline substances such as potassium hydroxide (KOH), sodium hydroxide, and ammonium hydroxide, and etchants (such as HF) can be used for this purpose.

Accordingly, there is a need for a method for treating an etched glass surface and/or for cleaning sludge from an etched glass surface that avoids re-contamination and/or introduces additional defects.

Disclosed herein are new, effective, safe, and environmentally friendly methods for treating glass surfaces after etching to remove sludge.

Disclosed herein is a method of treating an etched glass surface, the method comprising applying a solution comprising at least one mineral acid to the etched glass surface. In at least some embodiments, the etched glass surface has been previously etched using an etchant comprising fluoride ions. In certain embodiments, the cleaning solution is free of fluoride ions, such as ions from hydrofluoric acid.

Also disclosed herein is a solution for treating a surface of an etched glass, the solution comprising at least one mineral acid. In at least some embodiments, the solution is free of fluoride ions. Further disclosed herein is an etched glass surface that has been etched using an etchant comprising fluoride ions, the glass surface being prepared by a method comprising treating the etched glass surface with a solution comprising at least one mineral acid. .

The surface of the glass after etching (for example, using HF etching) may contain or be contaminated with insoluble sludge generated during the etching process. Sludge may be derived from metal ions from etched glass (eg, K ⁺ , Ca ²⁺ , Al ³⁺ , and Si ⁴⁺ ) and ions from etchants (eg, ammonium (NH ₄ ⁺ ) and fluoride (F ⁻ )) ) composed of. For example, sludge from glass and etchants may contain Ca ²⁺ , Al ³⁺ , and F ⁻ . Because the sludge is not soluble in either the base or the acid (such as HF used in traditional chemical cleaning solutions), the sludge particles will detach and then reattach to the chemical cleaning process using alkali and acid (eg HF). Glass surface. In this case, the current chemical method does not completely clean the glass surface because the re-attached sludge contaminants are still on the glass. In addition, chemical cleaning solutions may contain hazardous chemicals such as KOH and/or HF. Traditional chemical cleaning can be dangerous and waste disposal is expensive.

Therefore, it may be desirable to treat or clean the etched glass to recover a clean and stain-free surface of the glass. New methods have been developed to effectively clean glass surfaces after etching using etchants containing fluoride ions, the method comprising applying a solution comprising at least one mineral acid to the etched glass surface. The methods disclosed herein are capable of cleaning the etched glass surface in at least some embodiments without creating defects or reducing the strength of the glass. In various embodiments, the methods disclosed herein may also be cost effective, simple to operate, and environmentally friendly.

The foregoing general summary and the following embodiments are merely illustrative and are not limiting of the disclosure. Further features and variations may be provided in addition to those set forth in the description. For example, the disclosure describes various combinations and sub-combinations of the features disclosed in the embodiments. In addition, it should be noted that when the steps are disclosed, the steps need not be performed in the order disclosed, unless A clear statement.

Figure 1 shows the X-ray diffraction (XRD) spectrum of glass sludge produced from Eagle XG ^® glass and HF.

Figure 2 is a graph showing the etch rate of Eagle XG ^® glass in a used cleaning solution containing 6 M HCl and 12 g/L dissolved Eagle XG ^® glass sludge.

Figure 3 is a diagram showing the dissolution of Eagle XG ^® glass sludge at room temperature.

Figures 4A and 4B illustrate X-ray photoelectron spectroscopy (XPS) results for glass cleaned using different cleaning methods, including unetched glass, etched glass (ie, the glass is etched and then in deionized water) Rinse for 10 minutes), etched glass and rinse with deionized water plus mechanical agitation, etched glass and ultrasonic cleaning, etched glass and rinsed in 3M HCl, and etched glass in 6M HCl Cleaning. Fig. 4A illustrates the amounts of B, Al, Si, and F remaining on the surface of the glass after cleaning using an etching method. Fig. 4B is a view showing the amounts of N, Mg, and Ca remaining on the surface of the glass after cleaning using an etching method.

Figures 5A and 5B illustrate TOF-SIMS (Time of Flight - Secondary Ion Mass Spectrometry) results for glass cleaned using different cleaning methods, including unetched glass, etched glass (ie, glass is etched) Then rinse in deionized water for 10 minutes), etched glass and rinse with deionized water plus mechanical agitation, etched glass and ultrasonically cleaned, etched glass and cleaned in 3M HCl, etched glass and Cleaning, etched glass in 6M HCl and using horizontal scrubbing, etched glass Vertical scrubbing and etched glass were used and cleaned using a standard cleaning 1 ("SCl") million ultrasonic cleaning method. Figure 5A illustrates the residual amounts of Al, Si, K, Ca, O, and F. Figure 5B illustrates the residual amounts of B, Sr, and Mg.

6 after picture shows the different cleaning method of the surface strength of the glass surface of the comparison, a sample including initial drawing and Eagle XG ^® glass unetched, etched early baseline sample Eagle XG ^® glass, etched glass and cleaned by scrubbing, The glass is etched and cleaned by ultrasonic cleaning, and the glass is etched and rinsed by HCl.

After the etching process, such as etching using HF, the glass surface may still be considered dirty because the glass surface may contain sludge formed during the etching process. Therefore, it may be desirable to process or clean the surface of the glass that has been previously etched. Disclosed herein is a novel method of cleaning a glass surface after etching the glass surface using an etchant containing fluoride ions, wherein in at least some embodiments, the method may not create defects or scratches on the glass surface and/or Or the glass substrate can no longer be contaminated.

In certain embodiments disclosed herein, the glass surface is cleaned by dissolving sludge contaminants in the cleaning solution such that the sludge contaminants are chemically unable to reattach to the etched glass surface. In certain embodiments disclosed herein, the glass surface can be completely decontaminated and not recontaminated because the sludge is completely or substantially completely dissolved in the cleaning solution.

As used herein, "cleaning" refers to treating an etched glass surface in a manner that reduces the amount of sludge on the surface of the etched glass. "Used in this article" """ refers to exposing the glass surface and/or sludge to a cleaning solution. In at least some embodiments, the cleaning can include dissolving some or all of the surface sludge produced by etching the surface of the glass using an etchant comprising fluoride ions, such as HF. The etched glass surface can have been etched using any ionic etchant containing fluoride ions known to those of ordinary skill in the art. For example, in certain embodiments, the etched glass surface disclosed herein may have been used with HF, HF, and mineral acids, buffered HF (eg, ammonium fluoride and hydrofluoric acid), ammonium bifluoride, and ammonium fluoride. Etching with at least one of the at least one acid.

In certain exemplary embodiments, the solution disclosed herein for treating etched glass comprises at least one inorganic acid, such as a mineral acid that is more acidic than the etchant. In certain exemplary embodiments, the at least one mineral acid has a lower pKa than 3.16 pKa of HF. In still further exemplary embodiments, the concentration of the at least one mineral acid is at least about 3M, such as at least about 6M.

According to certain embodiments disclosed herein, may be used and non-limiting examples of inorganic acids include hydrochloric acid (HCl) and nitric acid (HNO _3). Sulfuric acid (H ₂ SO ₄ ) may be used in certain embodiments, such as embodiments in which the sludge is free of Ca ²⁺ . This is because H ₂ SO ₄ may react with Ca ²⁺ and produce insoluble calcium sulphate (CaSO ₄ ). However, it is contemplated that any inorganic acid having a pKa less than HF can be used when the etched glass surface is etched using HF.

The cleaning solution disclosed herein may further comprise at least one surfactant. In certain embodiments, the surfactant may aid in the detachment of sludge from the glass surface and/or suspend the sludge particles in the cleaning solution, although this is not required. In some embodiments, the suspended sludge particles can be dissolved more quickly in the cleaning solution comprising at least one surfactant. Exemplary surfactants that may be used in accordance with certain embodiments disclosed herein include fluorinated surfactants, such as FS-10 from DuPont. Other exemplary surface active agent may include anionic surfactant (e.g. sodium lauryl sulfate) and nonionic surfactant (e.g. Triton ^TM X-100).

In at least some embodiments, increasing the temperature of the cleaning solution disclosed herein can further speed up the cleaning process. In certain embodiments, the temperature of the cleaning solution can be room temperature or higher, such as at least about 22 °C, such as at least about 25 °C, or at least about 30 °C.

As discussed above, one component of the sludge produced by the cleaning process can include fluoride from the HF etching process. When the sludge is dissolved using a cleaning solution comprising at least one mineral acid as disclosed herein, the fluoride-containing sludge may be slightly dissociated first and release free fluoride ions at a certain concentration. A cleaning solution comprising at least one mineral acid contains a high concentration of protons (H ⁺ ) from inorganic acid ions. Protons can act as fluoride (F ^- ) ion scavengers and combine with F ^- ions to form water soluble HF. The depleted F ^- ion can then further promote sludge dissociation until the sludge is dissolved almost completely (or in some embodiments) into the cleaning solution.

The following formula 1 (EQ.1) represents a general mechanism for forming a glass sludge during a process of etching a glass surface using an etchant containing fluoride ions, wherein M represents a metal ion. Metal ions from the glass sludge are combined with fluoride ions from the fluoride etchant, and the compound (MF _n ) precipitates due to strong binding force.

EQ.1: M ⁿ⁺ +nF ^- →MF _n

Equation 2 (EQ.2) is the reverse reaction of EQ.1 and may also be referred to as a dissociation reaction. The glass precipitate (MF _n ) can be dissolved by the reaction shown in EQ.2.

EQ.2: MF _n →M ⁿ⁺ +nF ^- However, the dissociation of the glass precipitate (MF _n ) may be weak. Therefore, in order to promote dissociation of the glass precipitate, protons (from strong acids) may be added to capture free fluoride ions, as shown in Formula 3 (EQ.3): EQ.3: H ⁺ +F ^- → HF because from EQ The fluoride ion of .2 is continuously consumed by EQ.3 (i.e., in the presence of at least one inorganic acid), so that the reaction of EQ.2 can be shifted from the left to the right, and then the glass precipitate can be dissolved.

In certain embodiments, the method of cleaning glass disclosed herein can be used to clean sludge produced from the etching of any type of silicate-containing glass using HF. For example, in some embodiments, the display glass can be cleaned, such as a display glass for a liquid crystal display. In certain embodiments, the glass can be selected from the group consisting of aluminosilicate glass and borosilicate glass. In certain exemplary embodiments, may be washed Gorilla ^® glass, including for example, Gorilla ^® glass 2 and Gorilla ^® glass 3.

Certain embodiments disclosed herein may be beneficial in several respects, although such benefits are not required. For example, the methods disclosed herein can be relatively efficient because the cleaning solution can quickly dissolve sludge from the glass surface and thus clean the glass in a short period of time. By way of example only, in at least some embodiments, the cleaning solutions disclosed herein can be shorter than or equal to about The sludge is dissolved from the surface of the glass for a period of 25 minutes (e.g., shorter than or equal to about 10 minutes, or shorter than or equal to about 5 minutes). In certain exemplary embodiments, a large amount of glass sludge (eg, about 4 g/L) can be dissolved in about 5 minutes.

In still further exemplary embodiments, the methods disclosed herein may not physically damage the glass surface during the cleaning process or may reduce physical damage to the glass as compared to conventional chemical cleaning methods. Thus, the methods described herein can substantially maintain the glass surface without creating defects and/or reducing the strength of the glass surface.

Moreover, in at least some exemplary and non-limiting embodiments, the cleaning solutions disclosed herein may comprise only one inorganic acid, such as hydrochloric acid (HCl). In certain embodiments, the cleaning solutions disclosed herein comprise 3M, 4.5M, or 6M HCl.

In various other exemplary embodiments, the methods disclosed herein for treating an etched glass surface are relatively safe compared to conventional chemical cleaning methods because conventional chemical cleaning methods may be used at very high temperatures. HF and / or KOH, this may be dangerous. In certain embodiments, the cleaning solutions disclosed herein may be free of HF and/or KOH, and/or the process may be carried out at room temperature. Furthermore, since the cleaning solution disclosed herein may contain only inorganic acids, the cost of the raw materials is relatively low.

In certain exemplary embodiments, the methods disclosed herein for treating an etched glass surface produce HF in a cleaning solution. The cleaning solution used can therefore optionally be further used and/or recycled for etching additional glass surfaces. As disclosed herein, treating the etched glass surface with HCl can effectively remove fluoride residues from the etched glass surface, and Nor does it adversely affect the surface strength of the etched glass surface, such as, for example, conventional brushing.

In certain embodiments disclosed herein, the sludge may comprise at least one of F ⁻ and, for example, Al ³⁺ , Ca ²⁺ , Si ⁴⁺ , Mg ²⁺ , and Sr ²⁺ . In certain embodiments, the sludge can comprise at least one of AlF ₃ and SiF ₄ . In certain other embodiments, the main component of the sludge may be CaAlF _x, where x can range, for example, from about 3 to about 5, but not bound by this range. For example, in some embodiments, the main component of the sludge may be CaAlF _5. In certain embodiments, the secondary phase of the sludge can be MgAlF ₅ (H ₂ O) ₂ . In this regard, XRD spectra of the first exemplary glass sludge from the diagram of FIG 1 was dissolved in 6M HCl 3M HF and Eagle XG ^® glass. According to theory, the main peak at low angles may be CaAlF _x (where x is unknown), while the secondary phase of sludge is MgAlF ₅ (H ₂ O) ₂ .

As used herein, cleaning efficiency refers to the rate of dissolution of glass sludge in a cleaning solution. In certain embodiments disclosed herein, cleaning efficiency can be further improved by adjusting several factors. One factor that can improve the dissolution rate of the glass sludge is the type of inorganic acid used, since the cation from the inorganic acid may react with the glass sludge and inhibit the dissolution process. For example, in Eagle XG ^® glass sludge, when H ₂ SO _{4 is} used as the at least one inorganic acid, Ca ²⁺ from CaAlF _x reacts with SO ₄ ^2- and forms CaSO ₄ . However, it should be noted that in certain embodiments, H ₂ SO ₄ may be capable of dissolving sludge that does not contain sulfate-reactive metal ions (eg, Ca ²⁺ ). On the other hand, for example, HCl can dissolve Eagle XG ^® sludge very quickly because the chloride does not react with metal ions from the sludge.

Another factor that can improve the dissolution rate of the glass sludge is the concentration of the inorganic acid used. Increasing the concentration of the mineral acid can reduce the time required to dissolve the glass sludge. For example, in certain embodiments, the concentration of the mineral acid can be at least about 3 M, such as at least about 4.5 M or at least about 6 M. In at least one exemplary embodiment, the dissolving about 4g / L, Eagle XG ^® time the sludge may be improved by the concentration of HCl from about 3M to about 6M is reduced from about 80 minutes to about 10 minutes.

It should be noted that the addition of a fluoride ion source (e.g., HF) to the cleaning solution may slow the rate of dissolution. Thus, in at least some embodiments, the cleaning solution is substantially free of fluoride ions. For example, in certain embodiments, the cleaning solution is free of HF.

Another factor that can improve the dissolution rate of the glass sludge is the reaction temperature. In certain embodiments, the dissolution rate can be increased and the dissolution time shortened, for example, by increasing the reaction temperature from about 22 ° C to about 30 ° C or higher. In certain embodiments, agitation (e.g., agitation and/or ultrasonic treatment) may also accelerate the dissolution process because the reaction occurs at the interface of the solid (i.e., sludge) and liquid (i.e., cleaning solution).

In certain embodiments disclosed herein, the used cleaning solution can be further used to etch the glass surface by recycling. Reusing the cleaning solution to etch the glass surface can reduce the cost of raw materials and waste disposal. During the cleaning process disclosed in certain embodiments herein, the fluoride containing sludge may be dissolved in a mineral acid to produce HF in the cleaning solution during the cleaning process. In certain embodiments, the HF and mineral acid mixture in the used cleaning solution can etch the glass surface.

For example, in one exemplary embodiment, 1 L of 6 M HCl can dissolve approximately 16 g of Eagle XG ^® sludge. In another exemplary embodiment, the herein disclosed cleaning solution used in the etching rate of the glass Eagle XG ^® (produced by The 12g / L of Eagle XG ^® sludge was dissolved in 6M HCl) and was About 0.1 μm/min. See, for example, Figure 2, which illustrates the etch rate of the Eagle XG ^® glass etched using the used cleaning solution (6M HCl + 12g/L dissolved Eagle XG ^® sludge). In certain embodiments disclosed herein, the etch rate can be increased by adding additional fluoride ions to the used cleaning solution (eg, adding HF).

The methods disclosed herein have many advantages, including simplicity and low cost. The solutions disclosed herein can be applied to the etched glass surface by any method known to those of ordinary skill in the art. For example, the solution can be applied by dipping the etched glass surface into a solution or by spraying the solution onto the etched glass surface. In certain embodiments, immersing the glass in a cleaning solution at room temperature followed by rinsing in deionized water is sufficient to remove the glass sludge from the glass surface.

In certain embodiments disclosed herein, the cleaning methods disclosed herein can maintain the glass surface substantially defect free. The cleaning method disclosed herein protects the glass surface from scratches or other defects during the cleaning process without the need to use a brush to physically clean the glass surface.

All numbers used in the specification and claims are to be understood as being modified by the term "about" in all instances, unless otherwise indicated. It should also be understood that the precise numerical values used in the specification and claims are intended to constitute Efforts have been made to ensure the accuracy of the numerical values disclosed in the examples. However, any measurement The values will inherently contain some of the errors caused by the standard deviations found in the respective measurement techniques.

As used herein, the use of "a" means "at least one" and is not limited to "the one" unless the contrary is indicated.

It is to be understood that the foregoing general description

The accompanying drawings, which are incorporated in the claims, are in

Other embodiments will be apparent to those skilled in the art from this disclosure.

Instance

The following examples are not intended to limit the disclosure.

Example 1

The Eagle XG ^® sludge was dissolved in three different solutions: 15 wt% potassium hydroxide (KOH), 6 M HCl, and 10 wt% HF. 4 g/L of Eagle XG ^® sludge was added to each solution (ie, 0.2 g of Eagle XG ^® sludge was added to 50 ml of each solution). Eagle XG ^® sludge was completely dissolved in 6 M HCl in 10 minutes, resulting in a clear solution. The sludge remained insoluble in the other two solutions over several days, producing a clearly turbid solution.

Figure 3 illustrates the dissolution of Eagle XG ^® sludge in 6 M HCl at room temperature. As illustrated in Figure 3, during the dissolution process, metal ions (e.g., Ca ²⁺ , Al ³⁺ , and Mg ²⁺ ) are released from the sludge into the 6M HCl purge solution. The dissolution rate of Eagle XG ^® sludge can be obtained by monitoring the concentration of metal ions at different times. Calculations from changes in the concentration of Ca ²⁺ based on the dissolution process showed that nearly 65% of the sludge was dissolved in the first 2 minutes.

Example 2

Using 12% HF (i.e., 24% by volume of the stock solution 50 vol% HF) etching Eagle XG ^® glass, and using different cleaning method of the etched sheet. Cleaning with HCl confirmed that the fluoride residue was effectively removed from the surface without reducing the surface strength of the etched sample.

Etching was performed using 12% HF in an automated etching system. 10 "x 14" 1.1mm thick Eagle XG ^® sheet is thinned to 0.7mm, in addition to each of 200 micrometers on either side of the substrate of 400μm in total. Nitrogen was bubbled during the thinning and rinsing process. After thinning, the sheet was rinsed twice with deionized water, i.e., the sheet was rinsed for 5 minutes, then the rinsed water was discarded, and the sheet was rinsed for an additional 5 minutes with fresh deionized water. Then use the following different cleaning methods to clean the thinned sample: (1) rinse with deionized water for 5 minutes and use mechanical agitation; (2) wash with 4% semi-cleaned KG (KOH) detergent ultrasonic (40Khz) (3) rinsing with 3M HCl for 5 minutes; (4) rinsing with 6M HCl for 5 minutes; (5) using SC1 million ultrasonic cleaning with NH ₄ OH, H ₂ O ₂ , and H ₂ O; Bentler brush horizontal cleaning with 4% semi-cleaned KG (KOH) detergent; and (7) Bentler brush horizontal and vertical cleaning with 4% semi-cleaned KG (KOH) detergent.

Reference samples for the following three glasses were also used: (1) 10" x 14" pieces, thinned and rinsed in deionized water for 10 minutes; (2) 1.1 mm not thinned (as shown) 2" ×2" piece; and (3) brushed.

A side-light image of the reference sample and the cleaned 10x14" piece was taken. The cleaned 10x14" piece was cut into 2x2" pieces and analyzed. X-ray photoelectron spectroscopy (XPS) study (see Figures 4A and 4B) Figure) confirms the presence of calcium and fluorine on the unwashed (primarily thinned) surface. As shown in Figure 4, HCl consumes some of the Al on the surface and also removes fluorine from the surface. Ultrasonic washing is effective Fluoride residue was removed from the surface, but washing with mechanically agitated deionized water for another 5 minutes was not sufficient to wash away the residue.

TOF-SIMS analysis confirmed the presence of calcium, magnesium and fluorine on the surface of the etched sample and the sample rinsed with deionized water. See Figures 5A and 5B. As shown in Figure 5A, the 3M HCl solution consumed some of the Al on the surface and effectively removed the fluoride. Samples that were brushed horizontally and horizontally + vertically showed that potassium was present on the surface. Brushing is effective in removing fluoride residues, but there is some amount of potassium on the surface. It is possible that potassium is derived from the semi-cleaned KG detergent used in the brushing process.

Sidelight studies have shown that there are several scratches in the brushed sample. Optical microscopy images also support this observation. Optical microscopy images showed crystal formation in the surface of the initially etched and unwashed glass after a 10 week storage period. No crystal formation was observed in the washed samples. This further supports the importance of an effective cleaning method to remove fluoride residues left by the etching process.

All chemical treatments, including mechanically agitated deionized water rinses, 3M HCl rinses, 6M HCl rinses, ultrasonic cleaning, and millions of ultrasonic cleanings are at least removed from the etched glass surface. Partially effective. Brushing removes some chemical residues from the etched glass surface, but the brush can cause scratches and damage the surface quality of the glass substrate. An additional 5 minutes of deionized water rinsing is not sufficient to effectively remove fluoride residues from the glass surface. Even though the 6M HCl solution effectively removes fluoride residues, it also causes damage to the glass surface. 3M HCl has been shown to effectively clean the etched glass surface.

Example 3

A 10% HF (i.e., 20% by volume of the reservoir 50 vol% HF solution) 4 "× 4" size Eagle XG ^® sheet into a thickness of 300 microns and 500 microns from the sheet. These samples were washed using brushing, HCl washing, and ultrasonic cleaning. First test together with the reference sample and the surface strength of the etched glass samples of Eagle XG ^® First samples were drawn. As shown in Figure 6, the brushed sample has the lowest strength compared to the sample cleaned using the ultrasonic cleaning method and the initially etched reference sample. Among the tested cleaning methods, the HCl-washed sample had the highest strength. See Figure 6.

Table 1 below shows a summary of the cleaning methods used and the results of both surface quality and surface strength.

Example 4

Table 2 below shows the time and cleaning solution used to dissolve the Eagle XG ^® sludge. 4 g/L of Eagle XG ^® sludge was suspended in each solution for testing.

Claims (20)

A method of treating an etched glass surface that has been etched using an etchant comprising fluoride ions, the method comprising the step of applying a solution comprising at least one mineral acid to the etched glass surface. The method of claim 1, wherein the at least one inorganic acid is selected from the group consisting of hydrochloric acid, nitric acid, and sulfuric acid. The method of claim 1, wherein the at least one inorganic acid is hydrochloric acid. The method of claim 1 wherein the solution is substantially free of hydrofluoric acid prior to being applied to the etched glass surface. The method of claim 1 wherein the at least one mineral acid has a concentration of at least about 3M. The method of claim 1 wherein the at least one mineral acid has a concentration of at least about 4.5M. The method of claim 1, wherein the solution is applied to the etched glass surface for a period of time ranging from about 5 minutes to about 80 minutes. The method of claim 1, wherein the solution further comprises at least one surfactant. The method of claim 1 wherein the solution is applied at a temperature of at least about 22 °C. A treated etched glass surface that has been etched using an etchant comprising fluoride ions, the treated etched glass surface being prepared by a method comprising applying a layer comprising at least one mineral acid The solution is etched onto the surface of the glass. The treated etched glass surface of claim 10, wherein the at least one inorganic acid is selected from the group consisting of hydrochloric acid, nitric acid, and sulfuric acid. The treated etched glass surface of claim 10, wherein the at least one inorganic acid is selected from the group consisting of hydrochloric acid. The treated etched glass surface of claim 10, wherein the solution is substantially free of hydrofluoric acid prior to being applied to the etched glass surface. The treated etched glass surface of claim 10, wherein the at least one mineral acid has a concentration of at least about 3M. The treated etched glass surface of claim 10, wherein the at least one mineral acid has a concentration of at least about 4.5M. The treated etched glass surface of claim 10, wherein the solution is applied to the etched glass surface for a period of time ranging from about 5 minutes to about 80 minutes. The treated etched glass surface of claim 10, wherein the solution further comprises at least one surfactant. The treated etched glass surface of claim 10, wherein the solution is applied at a temperature of at least about 22 °C. A method of treating a surface of an etched glass, the glass surface having been etched using an etchant comprising fluoride ions, the method comprising the steps of: applying a solution comprising hydrochloric acid to the surface of the glass, the hydrochloric acid having a surface of at least about 3M The concentration, wherein the solution is substantially free of hydrofluoric acid prior to being applied to the etched glass surface. The method of claim 19, wherein the solution is applied to the etched glass surface for a period of time ranging from about 5 minutes to about 80 minutes.