Antimicrobial action of Cu, Cuo and Cu2O nanoparticles on glass surfaces and durable coatings

Cu, CuO and Cu₂Microbial action of O nanoparticles on glass surface and durable coating

[0001] Cross reference to related applications

[0002] According to 35U. SC § 119, this application requires the U.S. Provisional Application Series 61/468, 173 filed on March 28, 2011 and the U.S. Provisional Application Series 61/532 filed on September 8, 2011, The priority of No. 346 is based on this application and is incorporated herein by reference in its entirety.

Technical field

[0003] Embodiments of the present invention relate to the production of glass with antimicrobial activity on the surface, and particularly to glass surfaces containing copper and/or copper oxides. Embodiments of the present invention also relate to the manufacture of such copper-containing glass. Embodiments of the present invention also relate to a protective coating on the surface of the glass that does not inhibit the antimicrobial properties of the glass.

[0004] Background of the invention

[0005] The biological activity of copper is largely due to its ability to exist as metallic copper in the so-called "free" state or as copper salts or oxides in the so-called "ion" state. Although copper is almost always combined with other elements or minerals, in some cases, copper can exist in the state of ions or free copper, both of which are biologically active, thus giving copper to kill bacteria, viruses and The ability of the fungus.

[0006] Since ancient times, copper and its salts and oxides have been used to treat various diseases and injuries. The earliest recorded medical use of copper is recorded in the Egyptian medical book called the Smith Papyrus, written between 2600-2200 BC, which describes the use of copper to disinfect breast wounds and drinking water. Other early medical books such as the Ebers Papyrus (written around 1500 BC), Dioscride's De Materia Medica, and Orusco during the First Roman Empire Aulus Cornelius Celsus's De Medicina (De Medicina) and the works of Pliny and Hippocrates also describe copper in metallic form or as a salt or oxide. Medical use. The materials mentioned in earlier works include copper carbonate (possibly as the mineral malachite), copper chloride formed by the action of salt water on metallic copper, patina formed by the action of hot vinegar (acetic acid) vapor on metallic copper, and as sulfuric acid The bravery of copper. Copper in metallic form or as a salt or oxide is used to treat burns, itching headaches, tremor of limbs, boats and other diseases such as eye congestion, eye inflammation or congestion, cataracts, "intraocular fat" (possibly trachoma) and cataract. The Greeks used a dry powder mixture of copper oxide and copper sulfate, and also used red copper to oxidize It is a boiled mixture of copper oxide, (χο) and honey to treat wounds. Black copper oxide mixed with honey is used to get rid of roundworms, and its diluted form is also used to wake up the brain through nasal drops. When drinking as a mixture of honey and water, it is used as a stomach clearing agent, as an eye drop to relieve pain, and as a cleansing agent for oral ulcers. In the Americas, the Aztecs used copper and other ingredients The mixture was rinsed to treat sore throats. In India, copper was used to treat lung diseases, in ancient Persia, powdered copper carbonate was sprayed on the boat, and copper acetate and copper oxide were used for eye diseases. In addition, for hundreds of years Until now, it has been known that copper containers can be used to transport water without or hardly forming viscous substances. For the same purpose, when wooden or clay water containers are used as water containers, copper coins or copper bars are placed in the container, This particular practice was widely adopted by those who traveled in the western United States in the 19th century.

[0007] With the discovery of the existence of microorganisms in the 19th century, the antimicrobial properties of copper and its compounds have continuously been extensively studied, and these studies have continued to this day. Some examples of such documents include the following works: J· 0

Inactivation of influenza A virus on copper versus stainless steel surfaces by Noyce et al. Applied Environmental Microbiology, Vol. 73 (2007), No. 2748- 2750 pages; Mechanism of copper-media ted inac tivation of herpes virus by JL Sagripanti et al. Antimicrob Agents Chemotherapy, Vol. 41 (1997), No. 8122 -817 pages; Copper as a biocidal tool by G. Borkow et al." Curren t Med. Chem (Modern Medicinal Chemistry), Volume 12 (2005), pages 2163-2175; US Patent Application Publication No. 2001-0221307 (antiviral agents, antiviral fibers and antiviral fiber structures) Fiber structure)); US Patent No. 7192602, for Walter-insoluble, antimicrobial silicate glass and use thereof; and L. Esteban-Tejeda et al.^uAntibacterial and antifungal activity of a soda-lime glass containing copper nanoparticles Nanotechnology, Volume 20 (2009) 505701 (6 pages).

[0008] Although various forms of copper Cu° and copper ion Cubar as antimicrobial agents in various applications are mentioned, most of them are composed of reviews, and there is no actual description of specific properties on how to use copper substances. (See references below); for example, as membranes, solutions, particles, etc. See Copper as a biocidal tool by G. Borkow et al. Current Med. Chem, Vol. 12 (2005), pp. 2163-2175; N. Yamamoto et al., Biochem . Biophys. Acta. 2001, 91, 257; FT Jordan et al., Vet. Rec. 1971, 89, 609; and ATotsuka et al., Jpn. J. Microbiol. 1974, 1 & 107. In addition, only some documents mention that the effect of Cu° oxidation to CuO is the weakening of the antimicrobial effect of the substrate. The oxidation of Cu° to CuO is well known, and a protective film coating placed on top of the Cu° layer is usually used to prevent this oxidation. However, in addition to protecting the Cu° surface from oxidation, for antibacterial or antimicrobial use, the coating must not inhibit the antimicrobial or product's antimicrobial activity. In other words, an effective protective film is to protect the surface from oxidation while maintaining antibacterial or antimicrobial effects. There is no mention of using cuprous oxide Cu in or on glass₂0, especially Cu₂0 Nanoparticles act as an antimicrobial agent. In addition, there is no mention of products with a protective coating on copper nanoparticles, which can slow down or slow down the degradation of the antibacterial or antimicrobial activity of the nanoparticles.

[0009] In the past 20-30 years, touch screen devices have become popular in society, first appearing on automatic teller machines, and later on devices such as vending machines, mobile phones, computers, and personal electronic devices. With the increase in population density in cities and the high rate of population migration throughout the world, there has been concern about the spread of microorganisms. Although it is possible to remove or kill microorganisms by properly cleaning the surface with a suitable biocide, this is usually not a real practical solution, because many people will use a given device within a short period of time and cannot The device is continuously cleaned. Therefore, it is highly desirable to have surfaces that are durable and have antimicrobial properties for a period of time before cleaning them, so that different people using a certain device are equally protected. The embodiments of the present invention relate to this object.

Summary of the invention

[0010] Embodiments of the present invention relate to providing glass with Cu antimicrobial properties by depositing copper-containing nanoparticles on the surface of the glass. The way to achieve this goal is to add Cu, Cu in water or solvent₂0 or CuO nano-particle suspensions are dip-coated, spin-coated, slit-coated, curtain-coated or sprayed onto the glass surface. Then in air or inert atmosphere (such as nitrogen or ammonia)

Heat the glass to a temperature sufficient to seal the particles with the glass. In one embodiment of the method using CuO as the starting nanoparticles, the method includes subsequent steps to reduce CuO to Cu nanoparticles. The composition of the nanoparticles and the concentration of the nanoparticles on the surface of the transparent substrate (such as glass) determine the final light transmittance. Therefore, it is possible to provide an antimicrobial effect to originally transparent glass, including glass that has been thermally strengthened or chemically strengthened, for example, the smaller cations present in the glass are exchanged with larger cations in an ion exchange bath for chemical strengthening. In addition, it is possible to apply a coating of a material (such as a fluorosilane compound) that facilitates simple cleaning of the glass surface on the glass surface containing nanoparticles, or other coatings that resist fingerprint transfer or stains or minimize their effects. Layer without affecting the anti-microbial function. [0011] For Cu, CuO and Cu₂0, they all show antibacterial behavior at different surface concentrations, but only Cu shows antiviral behavior. Therefore, CuO is not an antiviral material. In order to have an antimicrobial effect when CuO is used as the starting nanoparticles, there must be a reduction step after sintering and/or ion exchange. Nanoparticles are reduced to Cu or Cu₂0 Nanoparticles. In one embodiment, the nanoparticles are reduced to Cu nanoparticles. The composition and concentration of Cu nanoparticles placed on glass or other substrates can be adjusted to optimize light transmittance, which can provide antimicrobial effects for originally transparent glass and chemically strengthened glass or other substrates.

[0012] In another embodiment, in the method, a final coating of an easy-to-clean material (such as a fluorosilane material) can be applied to the glass article after ion exchange without affecting the antimicrobial function of the article.

[0013] One embodiment of the present invention relates to an antimicrobial glass article, which has selected metal nanoparticles deposited on the surface of the glass, on which a selected protective layer is deposited, wherein the protective layer slows down Or slow down the degradation of the antimicrobial activity of nanoparticles. The oxidation of nanoparticles is the main reason why the antimicrobial activity of nanoparticles decreases or slows down. In one embodiment, the metal nanoparticles are selected from the group consisting of copper (0), silver (0), nickel (0), pincers (0), rake (0), gold (0) and zinc (0) Particles. The selected protective coating is selected from: sodium silicate (NaSil) and polysiloxane/silsesquioxane. In one embodiment, the glass article with nanoparticles and protective coating also has an easy-to-clean layer on top of the protective coating to help remove oil, such as fingerprint oil.

[0014] As described above, some embodiments of the present invention relate to methods of manufacturing glass articles having an antimicrobial metal nanoparticle surface and a protective coating on the metal nanoparticle surface/coating. In one embodiment, the method includes the deposition of the metal oxide nanoparticle coating by dip coating, spin coating, spray coating or other coating methods, which can deposit water or other suitable fluids on the glass surface. CuO or Cu₂0 Nanoparticle suspension, and allow the suspension to dry on the surface. Drying is performed in the temperature range of 100-150°C, preferably 110-130°C. The drying time is 1-4 hours. Then, a protective coating is deposited on the surface of the article containing oxide nanoparticles, and then a second drying step is performed in a temperature range of 120-300°C. The drying time is 1-4 hours. In the subsequent steps, the glass products with nanoparticles and protective coatings on them are sintered in air or an inert atmosphere (such as nitrogen atmosphere). If the glass contains exchangeable ions, an ion exchange process is performed to remove the surface from the glass. Compressive stress is reached to a selected depth, and finally hydrogen or other reducing gas or gas mixture is used for a reduction step to reduce oxide nanoparticles to copper.

[0015] In another embodiment, the method includes providing a mixture of copper oxide-containing nanoparticles and a protective material (with or without the fluid/nanoparticle suspension) suspended in a suitable fluid (such as but not limited to water) Surfactant and/or polymer carrier material), the mixture is deposited on the surface of the glass article and dried. Drying is performed in the temperature range of 100-150°C, preferably 110-130°C. The drying time is 1-4 hours. Nanoparticle/protective coatings with or without surfactants and/or polymeric carrier materials can be applied by spray coating, spin coating or dip coating. In the subsequent steps, the glass products with nanoparticles and protective coatings on them are sintered in air or an inert atmosphere (such as a nitrogen atmosphere). If the glass contains exchangeable ions, an ion exchange process is performed to remove the surface from the glass. Pressure to the selected depth

Shrinkage stress, and finally using hydrogen or other reducing gas or gas mixture for a reduction step to reduce the nanoparticles to copper.

[0016] The above-mentioned product and the protective coating in the preparation method of the product also play a role in making the nanoparticles adhere to the substrate. [0017] Embodiments of the present invention can provide many benefits for glass used in any "touch" application, such as but not limited to touch screens in mobile phones, computers, and ATMs. The glass in this type of application can be either ion-exchanged glass or non-ion-exchanged glass. Therefore, the technology provided in this article can be used to: provide antimicrobial activity for transparent glass used in applications that must be able to see through glass; provide antimicrobial activity for chemically strengthened glass; and when additional Functional coatings such as fluorosilanes or other coatings to enhance the cleanability of the glass, resist fingerprint transfer or smudges or minimize their effects, or provide anti-microbial properties when imparting hydrophobicity and/or oleophobicity active.

[0018] Ideally, all three properties are displayed to obtain an article or an article having a surface exhibiting antimicrobial behavior in strengthened glass, the touch surface of which has easy-to-clean properties and/or anti-smudge/anti-smudge properties. Fingerprint properties, and the glass is still transparent.

[0019] Brief Description of the Drawings

[0020] FIG. 1 is an X-ray diffraction pattern of glass prepared according to method 2 according to some embodiments.

[0021] FIGS. 2A, 2B, and 2C are SEM micrographs of glass surfaces prepared according to some embodiments.

[0022] FIG. 3A shows a flowchart of method A, the first method of preparing glass articles having metal or metal oxide nanoparticles thereon.

[0023] FIG. 3B shows a flowchart of the first method of preparing a glass article having metal or metal oxide nanoparticles thereon, method B, which combines the two steps shown in FIG. 3A.

[0024] FIG. 3C is a flow chart of the third method, method C, which can be used to prepare articles with metal nanoparticles, the protective material and the water-dispersible material are mixed together and sonicated, and then the mixture is deposited on the glass article on.

[0025] FIG. 4 is a graph of the absorption spectra of the Cu nanoparticle surface before and after 50Ό/50%RH (relative humidity) treatment.

[0026] FIGS. 5 and 6 are absorption spectra of samples of copper-containing nanoparticles in Table 1. In FIG. 5, only hydrogen reduction is performed, and in FIG. 6 after hydrogen reduction, treatment is performed at 50° C. and 50% RH.

[0027] FIG. 7A is a series of GI-XRD (grazing incidence/X-ray diffraction) spectra of samples with 2.5% by weight of Cu nanoparticles and NaSil protective coating after hydrogen reduction.

[0028] FIG. 7B is a GI-XRD spectrum of the sample in FIG. 6 after being processed at 50° C. and 50% RH.

[0029] FIG. 8 is an absorption spectrum of the copper-containing nanoparticle surface (sample 56-1, which is kept in water for 7 days) with a NaSil protective coating thereon. The samples were taken out of the water on the 4th and 7th days, and the absorption rate was measured. It shows that the Cu plasmon at 590nm decreases, because the sample is kept in water for a long time, and Cu is converted to Cu₂0 and/or CuO form.

[0030] Detailed description of the invention

[0031] All percentages herein are percentages by weight (wt%), unless otherwise stated.

[0032] The term "antimicrobial" as used herein refers to reagents or materials or surfaces containing reagents or materials that can kill or inhibit the growth of microorganisms from at least two groups of bacteria, viruses and fungi. The term used herein does not mean that it can kill or inhibit the growth of all microbial species in the family, but can kill or inhibit the growth of one or more microbial species from the family. When using "antibacterial", "antiviral" or "antifungal" to describe the reagent, it means that the test

The agent can only kill or inhibit the growth of bacteria, viruses or fungi. Commercially available Corning 2318 aluminosilicate glass (Corning Incorporated) was used to prepare all samples in this article. This article also uses the term NaS as the general term for sodium silicate, and the term "MS" as the general term for polysiloxane/silsesquioxane.

[0033] The term "logarithmic reduction" or "LR" as used herein means Log (Ca/C.), where C_aIs the number of colony forming units (CFU) on the antimicrobial surface containing Cu nanoparticles, C. Is the number of colony forming units (CFU) on the surface of the control glass without Cu nanoparticles. In other words,

[0034] LR=-Log(C_a/C₀）,

[0035] For example, a log reduction equal to 3 means that 99.9% of bacteria or viruses have been killed, and a log reduction equal to 5 means that T 99.999% of bacteria or viruses have been killed.

[0036] The present invention can be used to manufacture transparent cover glass for the following applications, such as, but not limited to, antimicrobial properties (the term "antimicrobial" is used to include all three of the following: antibacterial, antifungal, and antiviral) Touch screen device. In addition, for such antimicrobial applications, additional requirements are necessary. They include ways to maintain the following properties: surface cleanliness (treatment can severely limit antimicrobial activity) and chemical methods such as those provided by ion exchange ("IX") Mechanical strength, durability of any coating placed on the antimicrobial glass, and non-interference or minimal interference of any coating against microbial activity. Although it is well known that Ag and Cu can provide antimicrobial behavior to a certain extent, it is not always obvious how to combine the antimicrobial behavior with the two other properties mentioned above; in particular, how to accomplish this task to obtain Log reduction level> 3 (99. 9%) antimicrobial activity. It should be pointed out here that although the records of Ag and Cu antimicrobial activity are extensive, their specific descriptions vary greatly, from ionic solutions to doped glass coated with particles. For the applications pointed out in this article, we are talking about a smooth and transparent glass surface that can be made strong and cleanable in a way that produces obvious antimicrobial behavior. In addition, there are few (if any) literature reports that limit the level of activity in a strict manner, let alone for example the concentration of antimicrobial materials, particle size, etc.

[0037] In the present invention, we describe a method by which CuO nanoparticles can be deposited on glass, which can be IX strengthened and additionally coated with a fluorosilane layer to keep it clean , While maintaining a high level of antimicrobial behavior. No matter how it is done, Cu?. Or after the direct deposition of Cu nanoparticles, although the desired antimicrobial behavior is produced, this is not enough, because the subsequent IX treatment is highly oxidized and will cause Cu₂0 or Cu nanoparticles are oxidized back to CuO. CuO nanoparticles can show antibacterial properties, but they have only weak antiviral properties. In order to be described as antiviral, the material must have the antiviral activity against at least three viruses. In the present invention, we report that the antimicrobial glass described herein has antiviral activity against the following viruses: Viruses, HSV (herpes) and WSN (influenza A). In the present invention, we also report that the antimicrobial glass described herein has antibacterial activity against Escherichia coli.

[0038] One embodiment of the present invention relates to the antimicrobial properties of Cu present on the glass surface by depositing CuO-containing nanoparticles on the glass surface and reducing them to Cu nanoparticles. In another embodiment, it relates to Cu? present on the surface of the glass. The antimicrobial properties of nanoparticles, the presence of Cu on the glass surface. Nanoparticles can be realized by controlled oxidation of Cu nanoparticles on the glass surface. Can Cu₂A suspension of 0 or CuO nanoparticles in water is dip-coated, spin-coated or sprayed onto the glass surface, thereby completing Cu?. Or the deposition process of CuO nanoparticles. In one embodiment, the Cu₂0 or CuO nanoparticles are deposited, and then (in air or N₂Middle) The glass is heated to a temperature sufficient to seal or bond the nanoparticles with the glass. When CuO is used as the starting nanoparticles to be deposited on the glass and combined with it, there is a subsequent reduction step to reduce the CuO nanoparticles to Cu nanoparticles. In the examples herein, the reduction is performed in a hydrogen atmosphere. In another embodiment, after the reduction step, the Cu nanoparticles are processed in an autoclave to

Cu and Cu are formed on the glass surface₂0 A mixture of nanoparticles. The composition and concentration of the nanoparticles determine the final light transmittance.

[0039] Therefore, according to the guidance described herein, it is possible to provide antimicrobial effects for originally transparent glass and chemically strengthened glass. In one embodiment, the glass composition is selected from the group consisting of soda lime glass, alkali aluminosilicate glass, and alkali aluminoborosilicate glass. In another embodiment, after the nanoparticles are present on the glass surface in the form of Cu nanoparticles, the glass can be treated with fluorosilane materials to obtain a glass surface that can remove stains or other substances from the glass surface without damaging the glass surface. Easy-to-clean surface with anti-microbial properties. It should be understood that the antimicrobial properties described herein can be imparted to alkali aluminosilicate glass, alkali aluminoborosilicate glass, and soda lime glass, whether they are chemically strengthened or not. In addition, by using the method described herein, it is possible to: (1) start from chemically strengthened glass and impart antimicrobial properties to the glass; or (2) start from non-chemically strengthened glass, impart antimicrobial properties to the glass, and then pass Ion exchange chemically strengthens the glass.

[0040] Chemical strengthening of glass containing copper nanoparticles as an antimicrobial agent is not a simple process. When the reduced Cu nanoparticle sample is placed in ΚΝ0₃When the bath is chemically strengthened by ion exchange, the result is that when in the bath, the Cu nanoparticles are re-reduced to the CuO state. The re-oxidized CuO nanoparticles can be restored to the Cu state by repeating the H2 reduction step, but this is not a satisfactory solution because the reduction temperature of 450°C reduces the strength of the ion exchange glass by releasing the compression present in the glass. However, if it is necessary to perform ion exchange on glass containing reoxidized Cu nanoparticles, the effect of hydrogen reduction on chemical strengthening can be minimized by performing reduction at a lower temperature. For example, the reduction can be carried out in the temperature range of 250°C -350°C. For example, in an experiment, the reoxidized particles were reduced in hydrogen at 300°C for 5 minutes to 2 hours.

[0041] In the examples given herein, the colloidal copper (II) oxide dispersion (NanoArc® copper oxide, the average primary particle size powder is 23-37nm, 97.5%, Alfa Aesar, John Marze Company (Alfa Aesar, John Mathey Company) and the materials are dispersed in deionized (DI) water to produce colloidal suspensions of 0.5, 1, 2.5, and 5% by weight, where the size of the agglomerates is in the range of 100-200nm_oThen the colloidal suspension is subjected to ultrasonic treatment, which helps the fragmentation of the agglomerates, and then the dipping suspension draw speed of 10, 25, 50 and 100mm/min is used, and the alkaline aluminum silicon is dipped in varying concentrations. On the salt glass sample. The treatment of the coated glass further fractures the agglomerates, so that the glass is essentially coated with nanoparticles. In dip coating, contrary to intuition, generally the faster the pull-out speed, the thicker the coating thickness. It is also possible to use TERGITOL as a surfactant to prepare a suspension and apply it according to the method described above.

[0042] After the samples are dip-coated, they are dried at ambient temperature, such as in a laboratory fume hood, to facilitate air flow through the samples. A possible alternative drying method is, for example, but not limited to, drying in an oven with an air flow in the temperature range of 30° to 120°. After drying, the CuO nanoparticles are placed in an oven in a nitrogen atmosphere and sintered to a temperature of 600-650 Ό for a duration of 30 minutes to 4 hours. In one embodiment, sintering is performed at a temperature of about 625°C, and the duration is 1-2 hours. After sintering, the selected sample was reduced in a hydrogen atmosphere for 0.5-8 hours in a temperature range of 300-450°C. Can use H₂A mixture with an inert gas (for example, nitrogen or ammonia) is used for hydrogen reduction, or a commercially available forming gas can also be used. The reduction can also be carried out at an outlet pressure of 1-5 atmospheres, preferably 1-3 atmospheres. In one embodiment, when ion exchange is not required, the reduction is carried out at a temperature of about 450° C., and the duration is 1-5 hours. At this time, the glass has Cu nanoparticles on the surface and exhibits antimicrobial activity.

[0043] In one embodiment, the transparency of the glass product is greater than or equal to 70%; for example, greater than or equal to 80%, such as greater than or equal to 70%.

Example

[0044] Specific method for preparing antimicrobial glass

[0045] Method 1

[0046] a) Spin-coating, spray-coating or dip-coating CuO nanoparticles on glass that has undergone ion exchange or can be ion-exchanged (for example, Corning Glass No. 2318, 3318, 0210, which are commercially available). b) Heat the glass coated with CuO nanoparticles in %, ambient pressure (1 atmosphere) and 625-650°C for 0.5-1 hours to sinter (adhere or bond) the particles and the surface. (The sintering temperature depends on the glass composition). c) Chemically strengthen the sintered glass in a suitable ion exchange bath. d) Reduce CuO nanoparticles to Cu nanoparticles under medium pressure, ambient pressure (1 atmosphere pressure), and lower temperature (for example, a temperature of 300 Ό) for a duration of 5 minutes to 2 hours. e) Applying a fluorosilane coating to produce ion-exchanged glass with Cu nanoparticles thereon.

[0047] Method 2

[0048] a) As described in Method 1, CuO nanoparticles are spin-coated, spray-coated or dip-coated on latent ion-exchange glass (for example, Corning Glass No. 2318, 3318, 0210). b) As described in Method 1, heat the glass coated with CuO nanoparticles in% and ambient pressure (1 atmosphere) to sinter (adhere or bond) the particles and the surface together. The temperature depends on the glass. c) It is reduced to Cu nanoparticles (300°C) od) during ion exchange to strengthen the glass in c). e) Treated in an autoclave to produce Cu and Cu on it₂0 Nanoparticle ion-exchanged glass. Figure 1 is the X-ray diffraction pattern of the glass prepared according to method 2, the Cu nanoparticle peak is represented by 11, and Cu₂The 0 nanoparticle peak is represented by 10.

[0049] Method 3

[0050] a) As described in Method 1, CuO nanoparticles are spin-coated, spray-coated or dip-coated on latent ion-exchange glass (for example, Corning Glass No. 2318, 3318, 0210). b) Heating in air or nitrogen, the particles adhere to the surface and react with the glass (>600°C) oc) in %(450°C) to reduce to Cu nanoparticles. d) Apply fluorosilane coating.

[0051] FIGS. 3A, 3B, and 3C are SEM micrographs of the glass surface after the various stages listed above, according to some embodiments. In Figure 2A, 14 denotes CuO nanoparticles deposited on glass. In Figure 2B, 16 represents the glass surface after heating and sintering to 600°C, as described herein. In Figure 2C, 18 represents H at 300°C₂Cu nanoparticles after reduction.

[0052] Test result

[0053] I. Antibacterial

[0054] Definition: Log reduction=-Log(C_a/C₀), where Ca is the concentration of bacteria (or viruses or fungi) after contact with the antimicrobial surface, C_oIt is the concentration of the control bacteria that are not in contact with the antimicrobial surface.

[0055] For example: a log reduction equal to 5 means that 99.999% of bacteria have been killed.

[0056] Using Escherichia coli, the bacteria test was performed at a ratio of 1×10° bacteria/mL. Place the bacteria on the selected surface for 6 hours, and then count to determine the number of survived. The conditions are standard E. coli culture conditions. Table 1 below shows that for lxlO⁶Antibacterial behavior of bacteria/mL of E. coli in 6 hours. The CuO nanoparticles of samples 29-39 were prepared according to method 1, as shown in Table 1. No easy-to-clean coating is applied.

<td>sample</td><td>CuO wt%</td><td>speed</td><td>Log reduction</td>

<td>29</td><td>5</td><td>50</td><td>&gt;5</td>

[0058]

[0059]

[0060] Coating.

[0061]

<td>30</td><td>5</td><td>5()</td><td>&gt;5</td>

<td>31</td><td>2,5</td><td>50</td><td>&gt;5</td>

<td>32</td><td>2.5</td><td>50</td><td>&gt;5</td>

<td>33/34</td><td>1</td><td>5()</td><td>&gt;5</td>

<td>35</td><td>0.5</td><td>5()</td><td>&gt;5</td>

<td>36</td><td>0.5</td><td>50</td><td>&gt;5</td>

<td>37</td><td>0.5</td><td>50</td><td>&gt;5</td>

<td>38</td><td>().5</td><td>25</td><td>&gt;5</td>

<td>39</td><td>().5</td><td>25</td><td>&gt;5</td>

<td colspan="4">1. CuO wt% is the weight percentage of copper in the dip coating solution. 2. Speed = the speed of pulling out the glass from the dipping solution, the unit is nrni/min</td>

Table 1 Table 2 shows the test results of Escherichia coli obtained for 5 samples prepared according to Method 1. Easy to clean without application

<td>sample</td><td>CuO wt%</td><td>speed</td><td>Log reduction</td>

<td>132</td><td>1</td><td>50</td><td>&gt;5</td>

<td>133</td><td>1</td><td>50</td><td>&gt;5</td>

<td>134</td><td>1</td><td>50</td><td>&gt;5</td>

<td>135</td><td>1</td><td>5()</td><td>&gt;5</td>

<td>136</td><td>1</td><td>50</td><td>&gt;5</td>

<td colspan="4">1. CuO wt% is the weight percentage of copper in the dip coating solution.</td>

<td>2. Speed =</td><td colspan="3">The speed at which the glass is pulled out of the dipping solution, in mm/minute ο</td>

[0062] Table 2

[0063] Table 3 shows the test results of Escherichia coli obtained for 5 samples prepared according to Method 2, with fluorosilane as an easy-to-clean coating in some embodiments.

<td>sample*</td><td>CuO% at</td><td>650°C</td><td>H_:</td><td>Slam</td><td>Easy to clean</td><td>IX</td><td>Log reduction</td>

[0064]

<td></td><td></td><td>deal with</td><td></td><td>Kettle treatment</td><td>Floor</td><td></td><td></td>

<td>121</td><td>1</td><td>air</td><td>Yes</td><td>no</td><td>Yes:</td><td>no</td><td>&gt;5</td>

<td>122</td><td>1</td><td>air</td><td>Yes</td><td>no</td><td>no</td><td>no</td><td>&gt;5</td>

<td>174</td><td>5</td><td>air;</td><td>Yes</td><td>no</td><td>Yes</td><td>no</td><td>&gt;5</td>

<td>175</td><td>5</td><td>air</td><td>Yes</td><td>no</td><td>no</td><td>no</td><td>&gt;5</td>

<td>162</td><td>5</td><td>Ν,</td><td>Yes</td><td>Yes</td><td>no</td><td>no</td><td>&gt;5</td>

<td>163</td><td>5</td><td>ν₂</td><td>Yes</td><td>Yes</td><td>Yes</td><td>no</td><td>&gt;5</td>

<td colspan="8">For all samples, the speed of pulling the glass out of the dip coating solution was 50 mm/min. Ten = Cu and Cu⁺¹ ο</td>

[0066] Table 3

[0067] II. Anti-virus testing program

[0068] Viruses and cell lines

[0069] Adenovirus particles (Ad-CMV-eGFP) were purchased from Vector Biolabs (Philadelphia, PA) in Philadelphia, Pennsylvania. Herpes simplex virus type 1 was purchased from the American Type Culture Collection (ATCC). Influenza A virus (WSN strain) was provided by Tom Shenk of Princeton University. For adenovirus virus detection is performed in HeLa cells, VER0 cells are used for HSV, and MDCK virus is used for influenza viruses. HeLa, VERO and MDCK cell lines were obtained from ATCC. HeLa and VER0 cells were grown in Earle minimal essential medium (EMEM) supplemented with 10% fetal bovine serum (FBS), 4.5 g glucose per liter, 2 mM glutamine and antibiotics.

[0070] Anti-virus test

[0071] Place the glass slide sample in a polystyrene Petri dish (35mm). Set the final concentration to 10⁸A drop of 10 μL of virus solution diluted with D-PBS at PFU/mL was deposited on the center of the slide. Place the uncoated glass slide on top and press to spread the droplets between the glass slides. The virus is incubated at room temperature for 30 minutes to 1 hour. Then the slides in contact with the virus were thoroughly washed with 1 mL of D-PBS. Then dilute the virus with PBS (double serial dilution). Keep the sample on ice to maintain virus titer until virus inoculation.

[0072] Determination of virucidal activity

[0073] For influenza A virus and HSV, virus titer was determined by plaque experiment, and virus titer was determined by fluorescence microscopy for adenovirus.

[0074] HSV titer determination: the virus in contact with the glass sample was washed with EMEM with 2% FBS, and serially diluted in the same medium. The day before the test, a 24-well plate of freshly confluent Vero cells was prepared. Before inoculation with 0.2 mL of the diluted HSV suspension, the medium was removed from each well. In the incubator, at 37°C, the virus was adsorbed with 5% CO? for 75 minutes. Shake the board back and forth gently every 15 minutes. Then the virus suspension was removed and replaced with 1 mL of 0.4% agarose, EMEM2% FBS. Before placing the plate in the incubator, the agarose overlay was allowed to gel at room temperature for 1 hour. Board at 5%C0₂Incubate at 37°C for 72 hours in a humidified atmosphere. Viral infection is evaluated by plaque formation.

[0075] Influenza titer: with 0.2% BSA, 1% penicillin/streptomycin and 0.01% CaCl₂And MgCl₂D-PBS wash

The virus in contact with the glass sample is serially diluted in the same medium. The day before the test, a 24-well plate of freshly confluent MDCK cells was prepared. Before inoculation with 0.05 mL of the diluted HSV suspension, the medium was removed from each well and washed with the above-mentioned buffer. In the incubator, at 37°C, use 5% CO₂Absorb the virus for 60 minutes. Shake the board back and forth gently every 15 minutes. The virus suspension was then removed and replaced with 1 mL of 1% agarose, DMEM, 0.4% FBS, and 20 mM Hepes. Before placing the plate in the incubator, the agarose overlay was allowed to gel at room temperature. The plates were incubated in a humidified atmosphere of 5% (A) for 72 hours at 37°C. Viral infection was evaluated by plaque formation.

[0076] Adenovirus titer: wash the virus in contact with the glass sample with EMEM w/o serum and serially dilute it in the same medium. One day before the test, a 96-well plate of freshly confluent HeLa cells was prepared. Before inoculation with 0.05 mL of the diluted adenovirus suspension, the medium was removed from each well. In the incubator, at 37°C, use 5% CO₂Adsorb the virus for 20 hours. The virus suspension was then removed and replaced with 1 mL of EMEM, 10% FBS, 1% L-glutamine, and 1% penicillin/streptomycin. Board at 5%C0₂Incubate at 37°C for 24 hours in a humidified atmosphere. The virus infection was evaluated by fluorescence microscopy analysis.

[0077] Anti-virus activity calculation:

[0078] Log reduction=Log10 (titer virus control/titer virus sample)

[0079]% reduction=(1-(virus sample/virus control))*100

[0080] Table 4: Adenovirus

[0081]

<td colspan="2">sample*</td><td rowspan="2">Final potency after exposure (PFU/inL)</td><td rowspan="2">Reduction of virus titer%</td><td>Log reduction</td>

<td>Numbering</td><td>Evaluation</td><td></td>

<td>110</td><td>Cu and</td><td>0</td><td>100</td><td>4.62</td>

[0082]

<td></td><td>Cu₂Ot</td><td></td><td></td><td></td>

<td>109</td><td>Cu and Cu₂Ot·</td><td>0</td><td>100</td><td>4 62</td>

<td>114</td><td>Cut</td><td>0</td><td>100</td><td>4.62</td>

<td>113</td><td>Cuf ·</td><td>0</td><td>100</td><td>4.62</td>

<td>137</td><td>Cu and Cu₂O:;:</td><td>0</td><td>100</td><td>4.62</td>

<td>Control</td><td>No Cu</td><td>42090 soil 4889</td><td>0</td><td>0</td>

<td colspan="5">*=For all samples, the pulling speed from the dip coating bath is 50 mm/min. f = CuO is 1% by weight J = CuO Μ 5% by weightThe second surface is coated with an easy-to-clean material, such as fluorosilane.</td>

[0083] Table 5: HSV and influenza viruses

[0084]

<td colspan="2">sample*</td><td rowspan="2">Final potency after exposure (PFU/mL)</td><td rowspan="2">Reduction of virus titer%</td><td rowspan="2">Log reduction</td>

<td>Numbering</td><td>Evaluation</td>

<td>228</td><td>Cu and Cu₂Ot</td><td>0</td><td>100</td><td>4 05</td>

<td>220</td><td>Cu and Cu₂Ot</td><td>0</td><td>100</td><td>3.63</td>

<td>224</td><td>CuO ten</td><td>2100± 141</td><td>50</td><td>0 3</td>

<td>Control</td><td>No Cu</td><td></td><td>0</td><td>0</td>

<td colspan="5">Way = For all samples, the pulling speed from the dip coating bath is 50 blood hours and minutes. f = Cu is 1% by weight=The surface is coated with an easy-to-clean material, such as fluorosilane.</td>

[0085] Although the present invention has been described in terms of a limited number of embodiments, those skilled in the art can understand on the basis of understanding the benefits of the present invention that they can design designs without departing from the scope of the present invention disclosed herein. Other embodiments. Therefore, the scope of the present invention should be limited only by the appended claims.

[0086] In the following methods A-C, unless otherwise specified, the glass on which copper-containing nanoparticles and any additional materials such as protective materials, polymers or water-dispersible materials are deposited is Corning 2318 chemically strengthened glass, Among them, potassium ions exchange with sodium and lithium that may be present in the glass, thereby entering the glass.

[0087] Method A

[0088] In method A, as shown in FIG. 3A, water-dispersed copper-containing nanoparticles are deposited on the surface of the article by dip coating, spray coating or spin coating as shown by reference numeral 20, and then as shown by reference numeral 21 Shown in the temperature range of 100 Ό -150 Ό, so that the deposited particles are dried on the glass product. The drying time is 1-4 hours. Then, as shown by reference number 22, the glass product coated with nano-particles is coated with protective coating by spraying, dipping or spin coating, and then as shown by reference number 23, the product with the protective coating thereon is placed on Drying in the temperature range of 120Ό -300Ό. The drying time is 1-4 hours. Afterwards, as shown by reference numeral 24, in an atmosphere of air or inert gas (such as nitrogen or nitrogen), the nanoparticles and protective coating are sintered onto the glass product in a temperature range of 600°C to 700°C for a duration of 0°C. . 5-3 hours. In one embodiment, the temperature range is 600°C -650°C. Next, as shown by reference numeral 26, the sintered glass 24 is ion-exchanged using an ion exchange bath, which has a higher temperature than that present in the glass article. A large alkali metal ion. The ion exchange is carried out in the temperature range of 370°C to 450°C for a period of 10 minutes to 3 hours. After the ion exchange, the glass product is cleaned, and in a reducing atmosphere (such as hydrogen or forming gas), the metal nanoparticles on the glass are processed for 0.5-5 hours in a temperature range of 275 Ό -400 Ό, hydrogen or The pressure of other reducing gas is 1-5 atmospheres. In one embodiment, the reduction is carried out in hydrogen at a temperature ranging from 275°C to 325°C for 1 to 2 hours, and the hydrogen pressure is 1 atmosphere. In one embodiment, the glass article on which the nanoparticles are deposited as indicated by reference numeral 20 is an ion exchange glass article with compressive stress. Therefore, in the ion exchange process shown by reference numeral 26, the ion exchange

The alkali metal in 26 may have the same size as the alkali metal used to impart initial compressive stress. For example, if the glass product in 20 is a chemically strengthened glass prepared by potassium ion exchange sodium and/or lithium ions in the glass, Then potassium ions or larger ions can be used in processing step 26. Ion exchange indicated by 26 is performed to impart compressive stress to the protective coating and the glass.

[0089] As a specific example of the method A shown in FIG. 3A, a colloidal copper (II) oxide dispersion (NanoArc®, average particle size powder of 23-37 nm, 97.5%, Vigne, Pennsylvania was obtained) Alfa Aesar, John Mathey Company, Wayne, PA), and dispersed in deionized (DI) at a concentration of 0.5, 1, 1.5, 2.5, and 5 wt% ) In the water. The colloidal suspension was sonicated for 5-30 minutes, and then dip-coated on a sample of clean Corning 2318 glass (Corning). The concentration of the aforementioned nanoparticle suspension was used to prepare the nanoparticle-containing sample, reference numeral 20, The Corning 2318 glass is a chemically strengthened aluminosilicate glass. Dip coating is performed at 10, 25, 50, and 100mm/min dip coating pull-out speeds. In the dipping process, usually the faster the drawing speed, the thicker the coating thickness. The coated glass sample was then dried at 120°C for 2 hours (reference number 21), and then coated with a protective coating (reference number 22). Choose between two protective coatings. The first material is sodium silicate, also referred to herein as NaSil, with variable Si0₂Content and variable Si0₂/Na₂0 ratio (PQ Corporation, Malvern, PA), the second material is siloxane, in one embodiment, it is methyl siloxane (Honeywell, USA Morris Township, New Jersey (Honeywell Corporation, Morristown, Town)). Both materials obtained are diluted with their respective solvents to prepare a solution for dip coating. Using NaSil and MS, dip-coating glass products with nanoparticles on it at a varying speed (25-100mm/min). The sample was then dried at 300°C (reference number 23), and the nanoparticles and protective coating were sintered onto 2318 glass at 625°C in% for a duration of 1-2 hours (reference number 24). After sintering, use a KNO3 bath at a temperature range of 370°C to 450°C to perform ion exchange (IOX) for glass products with nanoparticles and protective coatings for 10 minutes to 3 hours, reference number 26, provided that the starting glass The product is chemically strengthened (ion exchange) glass. In one embodiment, the ion exchange is performed at a temperature of 420°C for a duration of less than 1 hour. In another embodiment, the time for ion exchange is less than 30 minutes. If the starting glass is not a chemically strengthened glass, ion exchange is carried out in the temperature range of 370Ό -450Ό for 5-8 hours. The typical ion exchange time and temperature are 420Ό and 5. 5 hours. After that, the obtained glass product can be used directly, or reduced in hydrogen or other reducing gas (for example, forming gas) at a temperature of 275°C to 350°C for 1-2 hours, as shown by reference numeral 28. In this example, after ion exchange, the selected sample is heated at 300°C in H₂Medium reduction for 1 hour.

[0090] Method B

[0091] Method B is shown in FIG. 3B. In this method, the steps denoted by reference numerals 20 and 22 in FIG. 3A are combined, and this combination is represented by reference numeral 30 in FIG. 3B. In the reference numeral 30 of FIG. 3B, the C^O or Cu nanoparticle dispersion and the protective material are mixed together, ultrasonically treated as described above, and then dipped, sprayed, spin-coated, or slit coating is used. Coating or co-deposition (simultaneous deposition) onto glass products. After the deposition is completed, the glass coated with nanoparticles and protective materials is first dried in the drying temperature range of 100°-150°C for a period of 1-4 hours (as shown by reference numeral 31), and then the coated glass is raised to 600Ό-700Ό sintering temperature (as shown by reference numeral 33), wherein the temperature is maintained for a period of 0.5-3 hours (as shown by reference numeral 34), the coating, nanoparticles and protective materials and glass products are sintered Or glued together. In one embodiment, the temperature range is 600 Ό -650 Ό. After the copper and the protective material are deposited, dried and sintered, the glass product is then ion exchanged (as shown by reference numeral 36), and hydrogen or other reducing gas is used in the The temperature range of 275°C-350°C reduces the nanoparticles for 1-2 hours (as shown by reference numeral 38). Depending on the antimicrobial application, the glass article may or may not undergo a reduction step. For example, after ion exchange, the system

The product is reduced at 300°C and 1 atmosphere for 1 hour. Using KNO3 bath, ion exchange is carried out in the temperature range of 370°C -450°C for 10 minutes to 3 hours. In one embodiment, the ion exchange is performed at a temperature of 420°C for less than 1 hour. In another embodiment, the time for ion exchange is less than 30 minutes. If the starting glass is not a chemically strengthened glass, ion exchange is carried out in the temperature range of 370°C -450°C for 5-8 hours, and the typical ion exchange time and temperature are 420°C and 5.5 hours.

[0092] Method C

[0093] In the method C shown in FIG. 3C, the Cu nanoparticles, the protective agent, and the water-dispersible material are mixed together and subjected to ultrasonic treatment, and then the Cu nanoparticles are treated by dip coating, spray coating, spin coating, or slit coating. The mixture is deposited on the glass article (as indicated by reference numeral 40). Then the glass product on which the material is deposited is dried in the drying temperature range of 100Ό -150Ό (as shown by reference numeral 41), and then heated in N2 or other inert gas atmosphere to the glass transition of the dispersible material than water The temperature Tg is lower than the selected temperature of 10-20°C (as shown by reference numeral 43), and when the temperature is lower than T_gThe selected temperature is maintained for a period of 0.5-3 hours (as indicated by reference numeral 44). After that, the obtained glass product can be used directly, or reduced in hydrogen or other reducing gas (for example, forming gas) at a temperature of 275°C to 350°C for 1-2 hours, as indicated by reference numeral 48. For example, after the exchange in Yuzi, the product is heated at 300°C and 1 atmosphere of H₂Medium reduction for 1 hour.

[0094] Protective coating (protective layer)

[0095] The silicate protective material used in the following table and drawings is sodium silicate E (153-x and 56-x series, PQ company), its SiO₂The content is 27.2% by weight, the remainder is water, Si0₂/Na₂The ratio of 0 is 3.2. Dilute different NaSil to different concentrations while ensuring a consistent and stable pH range of 11-12o. For this study, 153-1NaSi 1 is the most concentrated and 56-6 is the dilute used. For this coating, the effects of concentration and thickness are important parameters, because the ultimate goal is to anti-microbial while preventing oxidation. Use environmental conditions such as 50Ό/50%RH, and keep the sample immersed in water for 7 days to test the protective effect.

[0096] In addition to sodium silicate, alkylsiloxanes can also be used as a protective material. For example, dilute methylsiloxane Till (Accuglass resin, Honeywell Incorporated) with isopropanol, and also dip-coated on the CuO nanoparticle-coated surface as a Cu surface Evaluation on the protective layer. The material was found to be satisfactory. For the case of NaS custom paint, the influence of the concentration and thickness of methyl siloxane T11 is an important parameter, because the ultimate goal is to anti-microbial while preventing oxidation.

[0097] FIG. 4 is a 50°C/50%RH (relative humidity) treatment before (line 60) and after (line 62) absorption spectra of the Cu nanoparticle surface, which shows that the Cu plasmon is at 50°C/50%RH (relative humidity). After 50 treatment, a red shift occurred at 590 nm, with a wider and longer wavelength peak, and also showed a slope at shorter wavelengths below about 450 nm. It is believed that Cu is oxidized to Cu?. the result of. Sample S316 deposited 2.5% by weight of CuO nanoparticles on the glass surface. The sample is sintered at 650°C, ion exchanged, and then heated at 300°C in H₂Medium reduction for 1 hour.

[0098] The Cu nanoparticle surface was kept in water for 7 days, and the samples were taken out at 1, 4, and 7 days, dried, and their absorption was measured. It shows that the Cu plasmon at 590nm widens, drops and then disappears, because the sample remains in the water for a long time and is converted into Cu₂0 and/or CuO two forms. As mentioned above, to prepare glass, N at 650°C₂After sintering in an atmosphere, ion exchange is performed, and reduction is performed in an atmosphere of 300°C for 1 hour.

[0099] Figures 6 and 7 are the absorption spectra of the copper-containing nanoparticle samples in Table 6, after only hydrogen reduction (Figure 6), and after hydrogen reduction at 50°C and 50%RH. In each figure, the wide line represents the glass product after treatment at 50 °C and 50% RH, and the narrow line represents the glass product just prepared and before being immersed in water. Sample in hydrogen at 300°C

Perform 1 hour reduction.

[0100]

<td>sample#</td><td>CuO%</td><td>coating</td><td>NaSil curing</td><td>650N</td><td>3 ()0 Η</td><td>50°C/50% RH</td>

<td>618</td><td>1.5</td><td>56-4</td><td>1 Hours@120. (?/20 minutes@30(FC</td><td>650N</td><td>3 00 Η</td><td>5095()% RH for 2 hours</td>

<td>619</td><td>1.5</td><td>56-3</td><td>1 Hour@120°C/20 minutes@300°C</td><td>650N</td><td>3 00 Η</td><td>50°C/50% RH for 2 hours</td>

<td>620</td><td>1.5</td><td>56-1</td><td>1 Hours@120. (?/20 points</td><td>650N</td><td>3 OOH</td><td>5(). (/5()% RH2 hours</td>

[0101]

<td colspan="2"></td><td></td><td>Bell@30(rc</td><td></td><td colspan="2"></td>

<td>627</td><td>2.5</td><td>56-6</td><td>1 Hour@120°C/20 minutes(®300°C</td><td>650N</td><td>3 00H</td><td>50°C/50% RH for 2 hours</td>

<td>628</td><td>2.5</td><td>56-4</td><td>1 Hours@120. (?/20 minutes(®300°C</td><td>650N</td><td>300H</td><td>50°C/50% RH for 2 hours</td>

<td>629</td><td>2.5</td><td>56-3</td><td>1 Hours@120°C/20 minutes@30(rc</td><td>650N</td><td>3 00H</td><td>5095()% RH for 2 hours</td>

<td>630</td><td>2.5</td><td>56-1</td><td>1 Hours@120. (?/20 minutes@300°C</td><td>650N</td><td>3 00H</td><td>50°C/50% RH for 2 hours</td>

[0102] Table 6

[0103] FIG. 7A is a series of GI-XRD (grazing incidence/X-ray diffraction) spectra of samples with 2.5% by weight of Cu nanoparticles and NaSil protective coating after hydrogen reduction. Figure 7B is the GI-XRD spectrum of the sample in Figure 6 after being treated at 50°C and 50%RH. Table 7 describes the samples used to obtain the data in Figures 7A and 7B.

<td>sample</td><td>H,</td><td>50°C/50%RH</td>

<td>56-1</td><td>Cu (43.2, 50.5)</td><td>Cu (43.4, 50.6)</td>

<td>56-3</td><td>Cu (43.3, 50.4)</td><td>Cu (43.4, 50.6)Cu₂O (36.45)</td>

<td>56-4</td><td>Cu (43.3. 50.5)</td><td>Cu (43.2, 50.5)Cu₂O (36.3</td>

<td>56-6</td><td>Cu (43.2, 50.5)Cu₂O (36.5)</td><td>Cu (43.3) and quartz</td>

<td colspan="3">The sample contains 2.5% by weight of CuO and NaSil for a specific reduction at 300°C for 1 hour.</td>

[0105] Table 7

[0106] It can be seen from FIGS. 7A and 7B and Table 7 that the sample 56-1 with a higher NaSil concentration did not show oxidized copper species on the glass surface after being treated at 50° C. and 50% RH.

[0107] FIG. 8 is an absorption spectrum of the copper-containing nanoparticle surface (sample 56-1, which is kept in water for 7 days) with a NaSil protective coating thereon. The samples were taken out of the water on the 4th and 7th days, and the absorption rate was measured. It shows that the Cu plasmon at 590nm decreases, because the sample is kept in water for a long time, and Cu is converted to Cu₂0 and/or CuO form.

[0108] Antibacterial and Antimicrobial Testing

[0109] Table 8 shows the antibacterial test results after reduction of the Cu nanoparticle surface applied with the NaSil protective coating as described herein. The samples were prepared with two different CuO nanoparticle concentrations and varying protective coating concentrations as shown below. The test bacterium was Escherichia coli, the concentration was 10: bacteria/mL, the incubation time was 6 hours, and the temperature was 37°C. The sample was reduced for 1 hour at a temperature of 300°C.

[0110] Table 9 shows the antiviral test results using type 5 adenovirus (dEl/dE3), which is a non-replicating virus. The initial titer of the virus in contact with the sample glass or control slide shown with copper nanoparticles is 10⁶PFU/mL, contact time is 1-2 hours, room temperature (RT, 18°C -25£). The glass sample was cleaned with ethanol before setting the virus-containing titer, but was not processed in an autoclave.

[0111] Table 10 shows the different concentrations of NaSil used as a protective coating on the Cu surface.

[0112]

<td>Sample serial number</td><td>Dip coating conditions</td><td>After dipping</td><td>Log reduction</td>

<td>685</td><td>2.5% Cu, 100mm/min, 56-6</td><td>IX/restore</td><td>2.3</td>

<td>689</td><td>2.5% Cu, 100mm/min, 56-3</td><td>IX/restore</td><td>2.2</td>

<td>687</td><td>2.5% Cu, 100mm/min, 56-4</td><td>IX/restore</td><td>2.1</td>

<td>691</td><td>2.5% Cu, 100mm/min, 56-1</td><td>IX/restore</td><td>2.2</td>

<td>719</td><td>1 % Cu, 50inin/min 56-6</td><td>IX/restore</td><td>2.2</td>

<td>721</td><td>1 % Cu, 50mm/minute 56-4</td><td>IX/restore</td><td>2.2</td>

<td>723</td><td>1% Cu, 50mm/min, 56-3</td><td>IX/restore</td><td>2.3</td>

<td>725</td><td>1% Cu, 5()mm/min, 56-1</td><td>IX/restore</td><td>2.4</td>

<td>2318 Control</td><td></td><td></td><td>0</td>

<td>Soda Lime Glass</td><td></td><td></td><td>0</td>

<td>5%, 20 minutes Ag/K</td><td></td><td></td><td>&gt;5</td>

[0113]

<td>901BFK 10%Cu</td><td></td><td></td><td>&gt;6</td>

[0114] Table 8, Escherichia coli, antibacterial test

[0115]

<td>sample</td><td>Final titer after exposure (PFU/mL)</td><td>Virus titer reduced by%</td><td>Log reduction</td>

<td>618-1.5%CuO-650N/30()H-NaSi coating 56-4</td><td>2185 Soil 1150</td><td>99 07</td><td>2.03</td>

<td>618-1.5%CuO-65()N/30()H-NaSi paint 56-3</td><td>1610 ±593</td><td>99.31</td><td>2.16</td>

<td>618-1.5%CuO-65()N/300H-NaSi coating 56-1</td><td>3105 ±948</td><td>98.67</td><td>1.87</td>

<td>618-1.5%CuO-65()N/300H-NaSicoating 56-4</td><td>1840 Tu 751</td><td>99.21</td><td>2.10</td>

<td>618-1.5%CuO-65()N/300H-NaSi coating 56-3</td><td>1610 ±880</td><td>99.31</td><td>2.16</td>

<td>618-1.5%CuO-650N/30()H-NaSi coating 56-1</td><td>1495 Soil 1472</td><td>99.36</td><td>2.19</td>

<td>375-1.5% CuO-650N +IOX +/300H</td><td>1955 Soil 1472</td><td>99.16</td><td>2.08</td>

<td>2318 Control</td><td>235060 ±20715</td><td>0</td><td>0</td>

<td colspan="4">Sample 375 does not have a NaSil protective coating 2318 The control sample did not deposit any copper-containing nanoparticles on its surface</td>

[0116] Table 9, Adenovirus Type 5 (dEl/dE3) Test Results

[0117] NaSil protective coating concentration on Cu surface

[0118]

<td>NaSil number</td><td>Na₂O/SiO₂,Wt%/wt%</td>

<td>153-1</td><td>3.3/10.6</td>

<td>153-2</td><td>6.6/21.2</td>

<td>56-1</td><td>1.65/5.3</td>

<td>56-2</td><td>0.82/2.65</td>

<td>56-3</td><td>0.4/1.3</td>

<td>56-4</td><td>0.2/0.65</td>

<td>56-6</td><td>0.07/0.21</td>

<td colspan="2"></td>

[0119]

[0120]

[01211 Table 10: Coating as the final step, you can use the final coating of low surface energy coating to coat Cu-containing glass products, or Cu-Ag glass products, the coating is also called easy-to-clean coating Floor. For example, in many touch screen applications (mobile phones, computers, ATMs, etc.) where glass is used as a cover glass, a coating or film is applied to the glass surface to facilitate fingerprint removal. The coating that helps to clean is a low surface energy coating, for example, the general formula is A_x-Si-B₄__x"Fluorinated alkyl silane" type coating, where A is selected from the following group: perfluoroalkyl ΙζOne, perfluoroalkyl-terminated perfluoropolymethane, perfluoroalkyl-alkyl, fluoroalkene silane and Copolymer of vinyl silane and a mixture of fluoroalkyl silane and hydrophilic silane, B is C1, acetoxy group: CH₃-C(0)-O-] or alkoxy (for example -or. 2 out. -), x=1 or 2. The aforementioned types of low surface energy coatings can be purchased from different manufacturers, such as Dow Corning (Dow Corning) [DC2634-perfluoropolysilane, in which the functional perfluoro part is poly[oxy (1, 1,2, 2) , 3, 3-hexafluoro-1,3-propanediyl)], α-(heptafluoropropyl 1,2,2-tetrafluoro-3-(2-propenyloxy)propoxy], Gly Gelest [SIT8174. 0, Tridecafluorotetrahydrooctyltrichlorosilane, SIT8371.0, Trifluoropropyltrichlorosilane, SIH5841.0, Heptadecafluorotetrahydrodecyltrichlorosilane, and SIH5841.0, (heptadecafluoro-1, 1,2,2-tetrahydrodecyl) trichlorosilane&gt; SIH5841. 5, (heptadecafluoro-1, 1, 2, 2-tetrahydrodecyl) trimethoxy Base silane, and SIH5841. 2, (17 fluorine -1, 1, 2, 2-tetrahydrodecyl) triethoxysilane], Cytonix (Cytonix) [FSM1200 perfluoropolymonosilane, FSD2500 medium molecular weight perfluoropoly Disilane, FSD4500 high molecular weight perfluoropolysilane]-The low surface energy coating should have a spacer or skeleton chain ranging from 1nm-20nm, and the skeleton chain is carbon atoms or in the perfluoropoly In the case of , it is a combination of carbon atoms and oxygen atoms. In one embodiment, the chain length ranges from 2nm to 20nm. In another embodiment, the chain length is in the range of 1-10 nm. Other examples are

[0122] (a) Copolymers of fluoroalkenyl silane and alkenyl silane; and

[0123] (b) A mixture of fluoroalkylsilane and hydrophilic silane.

[0124] In addition to the aforementioned, silanes can also be used, provided that they do not hinder water vapor from reaching the glass surface, so that copper ions can be transported from the glass surface to the microorganisms, thereby killing the microorganisms or inhibiting their growth.

[0125] Generally, the above-mentioned fluorine-containing coating has one or two fluorocarbon-containing moieties connected to silane, and the chain length of each portion is unique.

Standing in the range of 1 nm to 20 nm, the chain may contain oxygen atoms or sulfur atoms along the chain. In one embodiment, the chain length ranges from 2nm to 20nm. In another embodiment, the chain length is in the range of 1-10 nm. The key to the coating is that at least part of the fluorocarbon part is far enough away from the surface, so that water molecules can contact the surface to obtain copper ions on the surface and transport the copper ions to the microorganisms. The copper ions are absorbed by the microorganisms to kill the microorganisms or reduce Its reproduction rate. Therefore, it is preferable that one or two fluorocarbon moieties are connected to a silicon atom, and the silicon atom is bonded to the glass through two or three Si-O bonds. For example, if the above-mentioned alkyl group (a) that acts as a spacer or backbone chain between the surface of the copper-containing glass and the fluorocarbon part is too short, the hydrophobic fluorocarbon part will block water molecules from reaching the glass surface, and the copper Ions cannot be transported from the surface to the microorganisms and enter them. Without wishing to be limited by theory, in another case, it is believed that the oxygen atoms in the perfluoropolyalkyloxysilane bound to the surface of the antimicrobial glass can promote water molecules to reach the surface through the oxygen atoms along the chain. It can coordinate with copper ions to promote ion transmission to microorganisms. An exemplary perfluoropolyoxysilane is Dow Corning (Dow Corning®) 2634, which is used as a fluorinated solvent in 0. 02-1% by weight solution. After the coating is applied to the antimicrobial glass article described herein, the coating is cured so that the coating adheres to the surface of the glass article, and finally sonicated in a bath of a fluorinated solvent (for example, NovecTM HFE7200 from 3M) Treat for 3 minutes to remove any unreacted paint. Heat curing of the coated product by heating the coated product in an oven, for example, at 50°C, 50% RH for the time recommended by the manufacturer, or by performing infrared heating on the coated product. The coated product can also be heated in an oven at 120°C for a period of 30 minutes to 2 hours to cure the coating material and the glass surface. Finally, the product was ultrasonically processed in HFE7200.

[0126] The method and process for depositing the coating can control the thickness and morphology of the coating on the glass surface. Processing methods and steps that allow the coating to be deposited in a discontinuous or nearly discontinuous manner can be introduced. The processing methods include, but are not limited to, vapor deposition or spraying through a predetermined cover, inkjet printing, micro-contact printing using a master mold (this method allows fluorosilane to be coated in a specific area), to achieve fluorosilane phase separation The moisture cures. When the coating is thin enough, it can be continuous. A thin continuous coating can be deposited by methods such as dip coating, spray coating, and vapor deposition, followed by adhesion to the silane by curing, and then ultrasonic cleaning to remove unreacted but physically adsorbed silane. The foregoing process achieves a sustained antimicrobial effect on open uncoated areas or areas with very thin coatings or uncoated surfaces, while maintaining the target functional properties of the coating. When the coating is continuous, the coating is thinner, and in one embodiment, the thickness ranges from 0.5 nm to 20 nm, so that the antimicrobial activity of the glass surface remains effective. In another embodiment, the thickness of the coating is 0. In the range of 5nm to 5nm. In another embodiment, the thickness of the coating is in the range of 1 nm to 3 nm. In the case of thin coatings, two silanes can be used to prepare a hybrid self-assembled monolayer on the surface, one of which is a fluoroalkyl silane and the other is a hydrophilic silane (for example, silane-containing polyethylene glycol ), in which hydrophilic or "water-loving" silane domains promote antimicrobial effects by capturing water molecules and transporting them to the surface. The water on the surface can obtain copper ions and transport them to microorganisms. In one embodiment, fluorine-oligoethylene glycol silanes can also be used, where the oligoethylene glycol portion of the silane can facilitate the capture of free water at the interface.

[0127] Glass composition

[0128] The provided glass products on which nanoparticles and protective coatings can be deposited are selected from soda lime glass, alkali aluminosilicate glass and alkali aluminoborosilicate glass products. In one embodiment, a 100% KΝ03 bath is used in the

Before the time of chemical strengthening 4-8 hours in the temperature range of 370Ό -450Ό, the glass provided is selected from the glass with the following composition:

[0129] (a) 60-70 mol% Si0₂&gt;6-14 mol%Α1₂0₃&gt;θ-15 mol%Β₂0₃&gt;θ-15 mol% Li₂0&gt;0-20 mol%Na₂0&gt;0-10 mol%K₂0&gt;0-8 mol% Mg0, 0T0 mol% CaO, O-5 mol% ZrO₂&gt;Ol mol% SnO₂&gt;Ol mol% CeO₂&gt;Less than 50ppm As₂0₃ And less than 50ppm Sb₂O₃^12 mol% W Li₂0+Na₂0+K₂0 W 20 motor

%, 0 mol% W MgO+CaO W 10 mol%;

(B) 64 mol% W SiO₂ W 68 mol%, 12 mol% W Na₂0 W 16 mol%, 8 mol% W Al₂0₃ W 12 mol%, 0 mol% WB₂0₃ W 3 mol%, 2 mol% W bird 0 W 5 mol%, 4 mol% W MgO W 6 mol%, and 0 mol% W CaO W 5 mol%, of which 66 mol% W SiO₂+B₂O₃+CaO W 69 mol%, Na₂O+K₂O+B₂O₃+MgO+CaO+SrO&gt; 10 mol%, 5 mol% 0 MgO+CaO+SrO W 8 mol%, (Na₂0+B₂0₃) -Al₂0₃ W2 mol%, 2 mol% 0 Na₂0-Al₂0₃ W6 mol%, and 4 mol% W (Na₂0+K₂0) -Al₂0₃ W 10 mol%;

(C) 61 mol% W Si0₂ W 75 mol%, 9 mol% W Na₂0 W 21 mol%, 7 mol% W Al₂0₃ W 15 mol%, 0 mol% WB₂0₃ W 12 mol%, 0 mol% W K2O W 4 mol%, 0 mol% W MgO W 7 mol%, and 0 mol% W CaO W mol%;

[0132] (d) 50 mol% WSi() 2W70 mol%, 8 mol%^Na₂0^ 16 mol%, 9 mol%^Al₂0₃ ^ 17 mol%, 2 mol% WB₂0₃ W 12 mol%, 0 mol% W "0 W 4 mol%, 0 mol% W MgO W 4 mol%, and 0 mol% W CaO W 0.2 mol%, wherein the alkali metal oxide and the alkaline earth metal oxide are Modifier, [(mol%Α1₂0₃+mol%B₂0₃) Ning Σ mol% modifier] ratio is greater than 1, namely:

[(Mol%Α1₂0₃+Β₂0₃) Σmol% modifier]&gt;1; and

(E) Si0₂&gt;50 mol%, 11 mol% W Na₂0 W 25 mol%, 7 mol% W Al₂0₃ W 26 mol%, οmol% WB₂0₃ W 9 mol%, 0 mol% W Κ2Ο W 2.5 mol%, 0 mol% W MgO W &amp; 5 mol%, and 0 mol% W CaO W 1. 52 mol%; wherein the foregoing various compositions basically do not contain lithium.

[0135] After chemically strengthening the aforementioned glasses, they have a compressive stress greater than 250 MPa. In one embodiment, the compressive stress is greater than 500 MPa. In another embodiment, the compressive stress is greater than 750 MPa.

[0136] In one embodiment, the transmittance of the glass product is greater than or equal to 70%; for example, greater than or equal to 80%, such as greater than or equal to 90%. In one embodiment, the transmittance of the glass article prepared according to method 1 is greater than or equal to 70%; for example, greater than or equal to 80%, for example, greater than or equal to 90%. Tables 11 and 12 correspond to various concentrations of CuO nanoparticles coated on glass using various dip coating pull-out speeds. The transmittance and haze were measured immediately after coating, after sintering, and after the reduction step. The transmittance and haze are measured based on ASTM D-1003 and ASTM D-1044. The broadband white light source corresponds to the CIE light source A (incandescent lamp) measured with HazeGuard PlusTM. The transmittance is the total amount of light passing through the sample, and the haze is 2.5. The amount of light scattered and transmitted outside the pyramid.

[0137]

Sample pull-out speed mm/min Freshly prepared sintered sintered reduced reduced haze% Transmittance% Haze% Transmittance% Haze% Transmittance%

<td>0.5% CuO</td><td>50</td><td>13.06</td><td>78.3</td><td>2.23</td><td>91.5</td><td>1.60</td><td>89.6</td>

<td>0.5% CuO</td><td>75</td><td>10.5</td><td>81.7</td><td>1.38</td><td>93.2</td><td>1.10</td><td>92.6</td>

<td>0.5% CuO</td><td>100</td><td>9.72</td><td>82.8</td><td>1.07</td><td>93.6</td><td>1.03</td><td>93.1</td>

<td>0.5% CuO</td><td>150</td><td>9.70</td><td>83.0</td><td>0.95</td><td>93.6</td><td>0.91</td><td>93.2</td>

<td>1%CuO</td><td>50</td><td>13.34</td><td>76.86</td><td>2.70</td><td>91.3</td><td>0.91</td><td>91.5</td>

<td>1%CuO</td><td>75</td><td>13.02</td><td>77.26</td><td>2.01</td><td>91.6</td><td>1.71</td><td>89.7</td>

<td>1%CuO</td><td>100</td><td>13.34</td><td>76.94</td><td>2.30</td><td>91.4</td><td>1.87</td><td>88.8</td>

<td>1%CuO</td><td>150</td><td>13.88</td><td>75.72</td><td>2.51</td><td>90.8</td><td>1.95</td><td>87.3</td>

<td>1.5% CuO</td><td>50</td><td>17.46</td><td>73.6</td><td>3.37</td><td>89.5</td><td>2.52</td><td>85.1</td>

<td>1.5% CuO</td><td>75</td><td>18.3</td><td>72.44</td><td>3.55</td><td>89.1</td><td>2.71</td><td>84.6</td>

<td>1.5% CuO</td><td>100</td><td>18.6</td><td>70.98</td><td>2.21</td><td>90.5</td><td>1.64</td><td>87.0</td>

<td>1.5% CuO</td><td>150</td><td>14.6</td><td>73.4</td><td>1.86</td><td>90.7</td><td>1.34</td><td>87.4</td>

<td>2.5% CuO</td><td>50</td><td>19.7</td><td>70.8</td><td>3.50</td><td>8&amp;3</td><td>2.37</td><td>85.0</td>

<td>2.5% CuO</td><td>75</td><td>18.3</td><td>73.7</td><td>2.68</td><td>89.6</td><td>1.97</td><td>86.2</td>

<td>2.5% CuO</td><td>100</td><td>18.0</td><td>72.4</td><td>2.41</td><td>90.6</td><td>2.20</td><td>86.3</td>

<td>2.5% CuO</td><td>150</td><td>17.4</td><td>67.3</td><td>4.08</td><td>85.9</td><td>3.06</td><td>79.0</td>

<td>5% CuO</td><td>50</td><td>18.5</td><td>68.3</td><td>3.77</td><td>87 ”5</td><td>3.00</td><td>80,4</td>

<td>5% CuO</td><td>75</td><td>13.4</td><td>58.7</td><td>6.65</td><td>75.8</td><td>4.34</td><td>58.0</td>

<td>5% CuO</td><td>100</td><td>14.8</td><td>55.9</td><td>7.95</td><td>72.8</td><td>5.71</td><td>52.4</td>

<td>5% CuO</td><td>150</td><td>11.2</td><td>51.3</td><td>7.44</td><td>5&amp;9</td><td>5.40</td><td>37.0</td>

[0138] Sintering conditions-650°, 1 hour, Ν₂in

[0139] Reduction conditions-300 Ό, 1 hour, out of

[0140] Table 11

[0141]

<td>sample</td><td>Pull out speed just made</td><td>Just made</td><td>Sintered</td><td>Sintered</td><td>Reduced</td><td>Reduced</td>

<td></td><td>Haze%</td><td>Transmittance%</td><td>Haze%</td><td>Transmittance%</td><td>Haze%</td><td>Transmittance%</td>

<td>0.5% CuO w/0.001% Tergitol</td><td>50</td><td>8.4</td><td>84.3</td><td>0.49</td><td>94.0</td><td>0.48</td><td>93.9</td>

<td>0.5% CuO w/ 0.001% Tergitol</td><td>75</td><td>6.9</td><td>86.3</td><td>0.31</td><td>94.2</td><td>0.35</td><td>94.2</td>

<td>0.5% CuO w/ 0.001% Tergitol</td><td>100</td><td>7.0</td><td>86.5</td><td>0.36</td><td>94.3</td><td>0.38</td><td>94.3</td>

<td>0.5% CuO w/0.001% Tergitol</td><td>150</td><td>9.6</td><td>81.9</td><td>0.50</td><td>94.0</td><td>0.48</td><td>93.8</td>

<td>1% CuO w/0.001% Tergitol</td><td>50</td><td>12.1</td><td>80.2</td><td>1.47</td><td>92.6</td><td>1.04</td><td>90.6</td>

<td>1% CuO w/0.001% Tergitol</td><td>75</td><td>11.8</td><td>81.1</td><td>1.15</td><td>93.1</td><td>0.88</td><td>91.5</td>

<td>1% CuO w/ 0.001% Tergitol</td><td>100</td><td>12.5</td><td>80.6</td><td>0.99</td><td>93.3</td><td>0.83</td><td>91.8</td>

<td>1% CuO w/0.001% Terqitol</td><td>150</td><td>13.6</td><td>79.8</td><td>1.03</td><td>93.2</td><td>0.84</td><td>89.8</td>

<td>1.5% CuO w/ 0.001% Terqitol</td><td>50</td><td>16.2</td><td>77.5</td><td>2.33</td><td>91.4</td><td>1.82</td><td>87.8</td>

<td>1.5% CuO w/0.001% Tergitol</td><td>75</td><td>12.0</td><td>81.5</td><td>0.89</td><td>93.6</td><td>0.72</td><td>92.6</td>

<td>1.5% CuO w/ 0.001% Tergitol</td><td>100</td><td>13.5</td><td>79.6</td><td>0.83</td><td>93.3</td><td>0.68</td><td>91.9</td>

<td>1.5% CuO w/0.001% Tergitol</td><td>150</td><td>15.6</td><td>77.3</td><td>1.06</td><td>92.7</td><td>0.92</td><td>90.1</td>

<td>2.5% CuO w/0.001% Tergitol</td><td>50</td><td>24.1</td><td>68.9</td><td>5.8</td><td>85.2</td><td>5.04</td><td>76.9</td>

<td>2.5% CuO w/ 0.001% Tergitol</td><td>100</td><td>22.5</td><td>63.2</td><td>7.27</td><td>80.2</td><td>577</td><td>69.1</td>

[0142] Table 12

[0143] For consumer electronic equipment, such as mobile phones, notebooks, tablet computers and similar small devices, including touch screen devices, the thickness of the final Cu-containing glass product is usually in the range of 0.2-52mni_oFor other uses, such as other applications used in antibacterial or antimicrobial shelves, desktops and hospitals, laboratories, and other institutions that handle microorganisms, the thickness can range from 0.5 mm to 2 cm, depending on the specific application.

[0144] Although typical implementations are presented for illustration, the foregoing description should not be considered as limiting the scope of the present or appended claims. Therefore, those skilled in the art can make various changes, modifications and substitutions without departing from the spirit and scope of this or the appended claims.